QM Notes Townsend PDF

Quantum Mechanics I & II Lecture Note
Daniel Erenso
February 26, 2019

ii
Contents
Introduction ix
I Quantum Mechanics I-PHYS 4380 1

1 Review of relevant topics 3
1.1 Vectors and Dirac notation . . . . . . . . . . . . . . . . . . . . . 3
1.2 Orthogonal matrices, the rotational operator, and Dirac notation 6
1.3 Eigenvalues and Eigenvectors . . . . . . . . . . . . . . . . . . . . 9
1.4 State vector, average, and standard deviation . . . . . . . . . . . 13
1.5 Magnetization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.6 Magnetic moment, angular momentum, and spin . . . . . . . . . 25
2 Stern-Gerlach Experiments 29
2.1 Virtual experiment by SG device . . . . . . . . . . . . . . . . . . 32
2.2 The spin quantum state vector . . . . . . . . . . . . . . . . . . . 35
2.3 Generalization for N-states system . . . . . . . . . . . . . . . . . 44
3 Rotation of Basis States and Matrix Mechanics 51

3.1 Matrix representation of the state vector . . . . . . . . . . . . . . 51
3.2 Rotation Operators . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.3 The identity and projection operators . . . . . . . . . . . . . . . 62
3.4 Matrix Representation of Operators . . . . . . . . . . . . . . . . 66
3.5 Changing representations . . . . . . . . . . . . . . . . . . . . . . 75
3.6 Expectation values using matrices . . . . . . . . . . . . . . . . . 80
3.7 The polarization state of a photon . . . . . . . . . . . . . . . . . 85
3.8 Birefregent crystals-like SG apparatus for photons . . . . . . . . 88
4 Angular Momentum 93
4.1 Commutation relations for the rotation operators . . . . . . . . . 93
4.2 None commuting operators and the uncertainty principle . . . . . 100
4.3 Commuting operators and the eigenstates . . . . . . . . . . . . . 105
4.4 Angular momentum eigenvalue equation . . . . . . . . . . . . . . 108
iii
iv CONTENTS
5 Time evolution of a quantum system 123

5.1 The evolution operators and the Schrödinger equation . . . . . . 123
5.2 Energy eigenvalue equation and the state vector . . . . . . . . . . 125
5.3 The Heisnberg and the interaction picture . . . . . . . . . . . . . 126
6 Interacting two spin-1/2 particles 143

6.1 Two particle basis states . . . . . . . . . . . . . . . . . . . . . . . 143
6.2 The electron-proton spin interaction . . . . . . . . . . . . . . . . 144
6.3 The addition of angular momenta . . . . . . . . . . . . . . . . . . 152
7 Wave mechanics in one dimension 157

7.1 From bra-ket vector to wave function . . . . . . . . . . . . . . . . 157
7.2 The dual particle-wave nature of matter . . . . . . . . . . . . . . 158
7.3 Plane waves and wave packets . . . . . . . . . . . . . . . . . . . . 160
7.4 The Schrödinger equation . . . . . . . . . . . . . . . . . . . . . . 165
7.5 The probability interpretation of the wave function . . . . . . . . 168
7.6 Expectation values in wave mechanics . . . . . . . . . . . . . . . 171
7.7 Where the momentum operator come from? . . . . . . . . . . . . 173
7.8 The wave function and the momentum space . . . . . . . . . . . 178
8 Classic 1-D quantum problems 187

8.1 Time independent Schrödinger equation . . . . . . . . . . . . . . 187
8.2 The Expansion postulate and its physical interpretation . . . . . 189
8.3 Particle in one dimensional box . . . . . . . . . . . . . . . . . . . 191
8.4 The step potential . . . . . . . . . . . . . . . . . . . . . . . . . . 201
8.5 The potential barrier and quantum tunnelling . . . . . . . . . . . 206
8.6 The potential well and bound states . . . . . . . . . . . . . . . . 212
9 The Harmonic oscillator 223

9.1 Classical Harmonic oscillator . . . . . . . . . . . . . . . . . . . . 223
9.2 Quantum harmonic oscillator-using the Schrödinger equation . . 224
9.3 The Harmonic oscillatorusing the ladder operators . . . . . . . . 231
10 Orbital angular momentum and hydrogenic atoms 243

10.1 Classical angular momentum . . . . . . . . . . . . . . . . . . . . 243
10.2 Quantum orbital angular momentum . . . . . . . . . . . . . . . . 244
10.3 The orbital angular momentum eigen functions . . . . . . . . . . 246
10.4 The Schrödinger equation and the orbital angular momentum . . 249
10.5 Hydrogenic atoms . . . . . . . . . . . . . . . . . . . . . . . . . . 251
II Quantum Mechanics II -PHYS 4390 261

11 Time-Independent Perturbation Theory 263
11.1 Nondegenerate and degenerate perturbation theory . . . . . . . . 263
11.1.1 Nondegenerate perturbation theory . . . . . . . . . . . . . 264
11.1.2 Degenerate perturbation theory . . . . . . . . . . . . . . . 271
CONTENTS v
11.2 PT application I - The Stark e¤ ect . . . . . . . . . . . . . . . . . 276

11.2.1 Hyrdogenic atom-review . . . . . . . . . . . . . . . . . . . 276
11.2.2 Stark E¤ ect in a Hyrdogenic atom . . . . . . . . . . . . . 279
11.3 PT application II -the real Hydrogenic atom . . . . . . . . . . . . 286
11.3.1 Relativistic Corrections . . . . . . . . . . . . . . . . . . . 287
11.3.2 Spin-orbit coupling correction . . . . . . . . . . . . . . . . 292
11.4 PT Application III -The Zeeman e¤ ect . . . . . . . . . . . . . . . 304
11.4.1 The anomalous zeeman e¤ect . . . . . . . . . . . . . . . . 305
11.4.2 The hiper…ne structure . . . . . . . . . . . . . . . . . . . 310
12 Many-particle systems 317

12.1 Many particle system Schrödinger equation . . . . . . . . . . . . 317
12.2 The two-particle system . . . . . . . . . . . . . . . . . . . . . . . 318
12.3 Identical particles and the exchange operator . . . . . . . . . . . 320
12.3.1 The exchange operator . . . . . . . . . . . . . . . . . . . . 320
12.3.2 The Pauli principle . . . . . . . . . . . . . . . . . . . . . . 322
12.4 The Helium atom–a two-fermion system . . . . . . . . . . . . . . 325
12.4.1 Perturbative approach . . . . . . . . . . . . . . . . . . . . 326
12.4.2 Variational approach . . . . . . . . . . . . . . . . . . . . . 340
13 Quantum …eld theory 345

13.1 Time dependent perturbation theory . . . . . . . . . . . . . . . . 345
13.2 Electromagnetic waves in vacuum . . . . . . . . . . . . . . . . . . 350
13.3 Monochromatic Plane waves . . . . . . . . . . . . . . . . . . . . . 351
13.3.1 The wave equation in terms of the potentials . . . . . . . 353
13.3.2 The vector potential for plane EM waves . . . . . . . . . 356
13.3.3 Energy of the electromagnetic …eld . . . . . . . . . . . . . 359
13.4 Canonical Quantization . . . . . . . . . . . . . . . . . . . . . . . 361
13.5 State of the electromagnetic …eld . . . . . . . . . . . . . . . . . . 363
14 Quantum description of charge-…eld interaction 367

14.1 Classical to quantum approach . . . . . . . . . . . . . . . . . . . 367
14.2 The dipole Approximation . . . . . . . . . . . . . . . . . . . . . . 369
14.3 Atom-…eld interaction Hamiltonian . . . . . . . . . . . . . . . . . 372
14.4 A single two-level atom and single mode …eld interaction . . . . . 374
15 Scattering 379
15.1 Expression of the Cross section . . . . . . . . . . . . . . . . . . . 379
15.2 The Born Approximation . . . . . . . . . . . . . . . . . . . . . . 379
15.3 An example of the Born approximation: The Yukawa Potential . 379
15.4 The method of Partial waves . . . . . . . . . . . . . . . . . . . . 379
16 Introduction to relativistic quantum mechanics 381

16.1 The Notations-Einstein’s notation . . . . . . . . . . . . . . . . . 381
16.2 Relativistic wave equation for spin-0 particles-the Klein-Gordon
equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
vi CONTENTS
16.3 Relativistic wave equation for spin-1/2 particles-the Dirac-equation 391
17 Intro to quantum informatics 393

17.1 Quantum bits and quantum entanglement . . . . . . . . . . . . . 393
17.2 Single Qubit gate . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
17.3 Multiple Qubit . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
17.4 Quantum Circuits . . . . . . . . . . . . . . . . . . . . . . . . . . 402
17.5 The no-cloning theorem . . . . . . . . . . . . . . . . . . . . . . . 403
17.6 Quantum entanglement and the Bell states-EPR pairs . . . . . . 405
17.7 Quantum Teleportation . . . . . . . . . . . . . . . . . . . . . . . 407
17.8 Quantum analyses of entanglement . . . . . . . . . . . . . . . . . 410
17.8.1 Entanglement by the entropy . . . . . . . . . . . . . . . . 411
17.8.2 Entanglement by the Concurrence . . . . . . . . . . . . . 416
17.9 Quantum analyses of teleportation …delity . . . . . . . . . . . . . 422
17.10Quantum Theory of a photon beam splitter . . . . . . . . . . . . 424
17.11A physical scheme for Quantum teleportation . . . . . . . . . . . 427
Preface
............
vii
viii PREFACE
Introduction
This is the lecture note for quantum mechanics I & II (PHYS 4380 & 4390) that
I used in Fall 2014 & Spring 2015. There will be signi…cant revision for the Fall
2018 and spring 2019.
ix
x INTRODUCTION
Part I
Quantum Mechanics
I-PHYS 4380
1
Chapter 1
Review of relevant topics
1.1 Vectors and Dirac notation

~ and B;
We recall that if the scalar product of two real vectors, A ~ is zero, given
by
X3
~ B
A ~ = Ai Bi = 0; (1.1)
i=1
the two vectors are said to be orthogonal. For a complex orthogonal vectors,
this becomes
X 3
~ B
A ~ = Ai Bi = 0; (1.2)
i=1
~ is the complex conjugate of A:

where A ~ Using Dirac notation any vector A ~ is
~
denoted by a ket vector jAi and its complex conjugate A by a bra vector hAj :
Then the dot product of two vectors, using Dirac notation, can be expressed as
3
X
hA jBi = Ai B i (1.3)
i=1
and if the vectors are orthogonal,

3
X
hA jBi = Ai Bi = 0: (1.4)
i=1
Orthonormal set of vectors: We recall the Cartesian unit vectors, x

^; y^; and
z^: These vectors are orthogonal
x
^ y^ = x
^ z^ = y^ z^ = 0 (1.5)
and have unit magnitude
j^
xj = x
^ x
^ = j^
y j = y^ y^ = j^
z j = z^ z^ = 1 (1.6)
3
4 CHAPTER 1. REVIEW OF RELEVANT TOPICS
Suppose, using Dirac-notation, if we represent these unit vectors as
je1 i = x
^; je2 i = y^; je3 i = z^ (1.7)
The Cartesian unit vectors satisfy the orthonormality condition
hej jei i = ij (1.8)
where ij is the Kronecker delta
1; i = j;
ij = (1.9)
0; i 6= j:
Generally a set of vectors fja1 i ; ja2 i ; ja3 i ; ::: jan ig satisfying the condition
haj jai i = ij (1.10)
are known as an orthonormal set of vectors.

In the vector space the Cartesian unit vectors form a complete set as any
vector, jAi ; can be expressed as linear combination of these orthonormal set of
vectors
jAi = A1 je1 i + A2 je2 i + A3 je3 i (1.11)
and
hAj = he1 j A1 + he2 j A2 + he3 j A3 (1.12)
so that
hA jAi = (he1 j A1 + he2 j A2 + he3 j A3 ) (A1 je1 i + A2 je2 i + A3 je3 i)

= A1 A1 he1 j e1 i + A2 A2 he2 j e2 i + A3 A3 he3 j e3 i
2 2 2
) hA jAi = jA1 j + jA2 j + jA3 j : (1.13)
Note that the quantity hA jAi represent the square of the magnitude of the
vector, that means
p q
~ 2 2 2
A = hA jAi = jA1 j + jA2 j + jA3 j : (1.14)
Furthermore we note that the components of the vector can be determined as
he1 jAi = A1 he1 je1 i + A2 he1 je2 i + A3 he1 je3 i = A1 ;

he2 jAi = A1 he2 je1 i + A2 he2 je2 i + A3 he2 je3 i = A2 ;
he3 jAi = A1 he3 je1 i + A2 he3 je2 i + A3 he3 je3 i = A3 : (1.15)
Orthonormal Sets of Functions: two complex functions, A(x) and B(x); are
said to be orthogonal for all x (a; b), when
Z b
A (x)B(x)dx = 0; (1.16)
a
1.1. VECTORS AND DIRAC NOTATION 5
where A (x) is the complex conjugate of the function A(x): A set of functions
fA1 (x) ; A2 (x) ; A3 (x) :::An (x) :::g (1.17)
that meet the requirement

Z b
0 m 6= n;
An (x)Am (x)dx = (1.18)
a C m = n;
where C is a constant, are said to form an orthogonal set of functions. Using

the Kronecker delta
0 n=6 m
nm = ; (1.19)
1 n=m
and Dirac notation, we may write
hAn (x) jAm (x)i = Cn nm (1.20)
For m = n,
hAn (x) jAn (x)i = Cn (1.21)
so that the for the set of functions de…ned by
An (x)
Fn (x) = p (1.22)
Cn
one can write

Z b
hFn (x) jFm (x)i = Fn (x) Fm (x) dx = nm : (1.23)
a
These set of functions are said to form an orthonormal set of functions.
Example 1.1 Show that the set of functions de…ned by
1
Fn (x) = p sin (nx)
for n = 1; 2; 3::::form an orthonormal set of functions for all x ( ; ).
Solution: Using Euler’s formula, we can express
1 eimx e imx
e inx
einx
Fm (x) = p sin (mx) = p ) Fn (x) = p (1.24)
2i 2i
so that
Z b
hFn (x) jFm (x)i = Fn (x) Fm (x) dx (1.25)
a
becomes
Z inx
e einx eimx e imx
hFn (x) jFm (x)i = p p dx
2i 2i
Z
1
= ei(m n)x e i(m+n)x
ei(m+n)x + e i(m n)x
dx
4
1 ei(m n)x e i(m+n)x ei(m+n)x e i(m n)x
= +
4 i m n m+n m+n m n
1 4 sin ((m n) ) 4 sin ((m + n) )
) hFn (x) jFm (x)i = ;
4 m n m+n
(1.26)
whether m = n or m 6= n the second term is always zero and we can write
sin [(m n) ]
hFn (x) jFm (x)i = = nm ;
(m n)
where we have applied applied Le Hospital rule. But it would be shorter
if one applies the double angle relations
cos ( + ) = cos ( ) cos ( ) sin ( ) sin ( ) ;
cos ( ) = cos ( ) cos ( ) + sin ( ) sin ( ) ;
that give
1
sin ( ) sin ( ) = [cos ( ) cos ( + )] :
2
In view of these relation, one can write the integral as
Z
hFn (x) jFm (x)i = sin (nx) sin (mx) dx
Z
1
= [cos ((n m) x) cos ((n + m) x)] dx (1.27)
2
1 sin ((n m) x) sin ((n + m) x)
= (1.28)
2 n m n+m
1 sin ((n m) ) sin ((n + m) )
= (1.29)
n m n+m
whether m is equal to or di¤erent from n; sin ((n + m) ) = 0; thus
1 sin ((n m) )
hFn (x) jFm (x)i = = nm
n m
1.2 Orthogonal matrices, the rotational opera-

tor, and Dirac notation
Matrices that make an orthogonal transformation of vectors. In an orthogonal
transformation of vectors the magnitude of the vectors remains the same. For
1.2. ORTHOGONAL MATRICES, THE ROTATIONAL OPERATOR, AND DIRAC NOTATION7
an orthogonal matrix
1
M = MT (1.30)
The rotational matrix R that we derived in Theoretical Physics I is an orthogonal
matrix. The rotational matrix is the matrix that transforms the Cartesian
X Y Z coordinate system to X 0 Y 0 Z 0 coordinate system by making a
counter-clockwise rotation about the z-axis by an angle (See Fig. 1.1). Such
Figure 1.1: A counter-clockwise rotation of the Cartesian coordinate about z-

axis by an angle :
a rotation transforms for example the position the vector ~r to ~r0 ; according to
r0 = Rr
0 1 0 10 1
x0 cos ( ) sin ( ) 0 x
) @ y 0 A = @ sin ( ) cos ( ) 0 A@ y A: (1.31)
z0 0 0 1 z
Next we re-formulate this rotation using Dirac notation and also by intro-
ducing an operator R^ ( ) which basically describes the operation we do to the
vector ~r in the x y z coordinate system in order to transform it to ~r0 :To this
end, we recall the basis vectors (or unit vectors) for the x y z coordinate
system,
je1 i = x
^; je2 i = y^; je3 i = z^ (1.32)
and also represent x; y; and z by x1 ; x2 ; x3 ; so that using Dirac notation, one
can write the vector ~r as
jri = x1 je1 i + x2 je2 i + x3 je3 i : (1.33)
Similarly, in the rotated new coordinate system (X 0 Y 0 Z 0 ) this vector is ~r0
an is given by
jr0 i = x01 je01 i + x02 je02 i + x03 je3 i : (1.34)
Figure 1.2: Coordinate rotation using Dirac formulation.
where
jr0 i = R^ ( ) jri = R
^ ( ) [x1 je1 i + x2 je2 i + x3 je3 i]
0 ^
) jr i = x1 R ( ) je1 i + x2 R^ ( ) je2 i + x3 R
^ ( ) je3 i : (1.35)
In order to see what this leads to, we need to understand what actually the
rotation operation mean so that we would be able to come up with the resulting
expressions for the action of the rotation operator on the basis vectors je1 i ; je2 i ;
and je3 i : From Fig. 1.2, we note that due to the rotation, we have
^ ( ) je1 i = cos ( ) je0 i sin ( ) je0 i ;
R 1 2
^ ( ) je2 i = sin ( ) je0 i + cos ( ) je0 i ;
R 1 2
^ ( ) je3 i = je0 i :
R (1.36)
3
so that
jr0 i = x1 (cos ( ) je01 i sin ( ) je02 i) + x2 (sin ( ) je01 i + cos ( ) je02 i) + x3 je03 i
) jr0 i = [x1 cos ( ) + x2 sin ( )] je01 i + [x2 cos ( ) x1 sin ( )] je02 i + x3 je03 i :
and recalling that
jr0 i = x01 je01 i + x02 je02 i + x03 je3 i : (1.37)
one …nds
x01 = x1 cos ( ) + x2 sin ( ) ; x02 = x1 sin ( ) + x2 cos ( ) ; x03 = x3
0 0 1 0 10 1
x cos ( ) sin ( ) 0 x
) @ y 0 A = @ sin ( ) cos ( ) 0 A @ y A ;
z0 0 0 1 z
1.3. EIGENVALUES AND EIGENVECTORS 9
where we used matrix representation.
1.3 Eigenvalues and Eigenvectors

In general, a linear transformation of a vector, ~r; to a vector, ~r0 ; using matrix
can be expressed as
~r0 = M ~r: (1.38)
In Cartesian coordinates
0 0 1 0 10 1
x M11 M12 M13 x
@ y 0 A = @ M21 M22 M23 A @ y A : (1.39)
z0 M31 M32 M33 z
Under this transformation if the vector ~r0 is expressible as

~r0 = M ~r = ~r; (1.40)
where is a constant, then the vector ~r is called the eigenvector (characteristic
vector) and is the eigenvalue (characteristic value) of the Matrix M;
0 10 1 0 1
M11 M12 M13 x x
@ M21 M22 M23 A @ y A = @ y A : (1.41)
M31 M32 M33 z z
Using the identity matrix, I;
0 1
1 0 0
I=@ 0 1 0 A; (1.42)
0 0 1
one can put Eq. (1.41)

0 10 1
M11 M12 M13 x
@ M21 M22 M23 A @ y A
M31 M32 M33 z
0 10 1 0 10 1
1 0 0 x 0 0 x
= @ 0 1 0 A@ y A = @ 0 0 A@ y A (1.43)
0 0 1 z 0 0 z
which can be rewritten as
20 1 0 13 0 1
M11 M12 M13 0 0 x
4@ M21 M22 M23 A @ 0 0 A5 @ y A
M31 M32 M33 0 0 z
=0 (1.44)
0 10 1
M11 M12 M13 x
)@ M21 M22 M23 A @ y A = 0:
M31 M32 M33 z
The eigenvalues are obtained from the condition

M11 M12 M13
M21 M22 M23 = 0; (1.45)
M31 M32 M33
which is known as the eigenvalue equation (characteristic equation). To …nd the
eigenvectors we substitute the eigenvalues and solve the resulting equations.
From The VNR Concise Encyclopedia of Mathematics (Van Nostrand Rein-
hold Co., publishers, 1977):
Eigenvalues: Eigenvalue problems are important in many branches of physics.
They make it possible to …nd coordinate systems in which the transformations
in question take on their simplest forms. In mechanics for instance, the prin-
cipal moments of a rigid body are found with the help of the eigenvalues of the
symmetric matrix representing the inertia tensor.... Eigenvalues are of central
importance in quantum mechanics, in which the measured values of physical
“observables” appear as the eigenvalues of certain operators. The term “trans-
formation” is used predominantly in pure mathematical (geometrical) context,
whereas “operator” is more customary in applications (physics, technology).
Example 1.2 Find the eigenvalues and the corresponding eigenvectors of the
matrix 0 1
0 1 0
M =@ 1 0 0 A (1.46)
0 0 0
Solution: The eigenvalue equation
0 1 0
0 1 0
1 0 0 =0) =0
0 0
0 0 0
3
) + =0) 1 = 0; 2 = 1; 3 = 1: (1.47)
The corresponding eigenvectors are determined from
0 10 1
M11 i M12 M13 xi
@ M21 M22 i M23 A @ yi A = 0: (1.48)
M31 M32 M33 i zi
For 1 = 0, we …nd
0 10 1
0 1 0 x1
@ 1 0 0 A @ y1 A = 0 ) x1 = 0; y1 = 0: (1.49)
0 0 0 z1
We use the bra-ket notation to represent eigenvectors. The eigenvector for
an eigenvalue, ; is represented using a ket-vector, j i ; which is expressed
as a column matrix 0 1
x
j i = @ y A: (1.50)
z
1.3. EIGENVALUES AND EIGENVECTORS 11
The eigenvector for 1 can then be written as a column matrix

0 1
0
j 1i = @ 0 A : (1.51)
z1
The corresponding bra-vector, h j ; generally, is the transpose conjugate
of the ket-vector. But here since we will consider only real values, the
bra-vector is written as
h 1j = x y z : (1.52)
Thus we can write
h 1j = 0 0 z1 : (1.53)
Both bra and ket vectors must be normalized (be unit vectors). Thus for
any eigenvectors, we must have
h j i = 1:
Normalizing this vector
0 1 0 1
0 0
h 1 j 1i =1) 0 0 z1 @ 0 A = 1 ) z1 = 1 ) j 1i =
@ 0 A:
z1 1
(1.54)
Similarly for 2 =1
0 10 1
1 1 0 x2
@ 1 1 0 A @ y2 A = 0 ) x2 + y2 = 0; x2 y2 = 0; z2 = 0
0 0 1 z2
) x2 = y2 ; z2 = 0 (1.55)
and the eigenvector becomes
0 1
1
j 2 i = x2 @ 1 A ; (1.56)
0
0 1
1
h 2 j 2i = 1 ) x22 1 1 0 @ 1 A = 1 ) x2 = p1 (1.57)
0 2
0 1
1
1 @ A
) j 2i = p 1 (1.58)
2 0
and for 3 = 1
0 10 1
1 1 0 x3
@ 1 1 0 A @ y3 A = 0 ) x3 + y3 = 0; x3 + y3 = 0; z3 = 0
0 0 1 z3
) x3 = y3 ; z3 = 0 (1.59)
0 1 0 1
1 1
1 @
) j 3 i = y3 @ 1 A ) j 3i = p 1 A: (1.60)
0 2 0
Using Mathematica:
Eigenvalue equation for Hermitian Matrices: A Hermitian Matrix is a matrix

that is equal to its transposed and conjugated matrix
T
(M ) = M: (1.61)
The eigenvalues for a Hermitian matrix are all real and the corresponding eigen-
vectors are orthogonal. This means for a Hermitian matrix with the eigenvalue
equation
M j ii = i j ii ; (1.62)
we always …nd
i = i (1.63)
and
0 i 6= j
h j j ii = = ij (1.64)
1 i=j
1.4. STATE VECTOR, AVERAGE, AND STANDARD DEVIATION 13
The Similarity Transformation: The similarity transformation of the matrix

M is given by
D C 1 M C: (1.65)
where C is a matrix whose columns are the eigenvectors of the Eigenvalue equa-
tion for matrix M . The matrix D is a diagonal matrix where the diagonal
elements are the eigenvalues.
1.4 State vector, average, and standard devia-

tion
Dirac’s notation is the easiest and most e¢ cient way of formulating quantum
mechanical processes as we shall see frequently in the …rst part of this course.
But I would like to show you …rst how Dirac’s notation can also be used other
than quantum mechanics by formulating two games: "a coin game" and "a Dice
game" using Dirac notation.
A coin toss: This game involves tossing a penny. A penny has two sides
which we usually call it head and tail. Suppose we represent the head side
by ja1 i and the tail side by ja2 i (see Fig.1.3). Let’s play the game like this,
every time the outcome of the game is head (ja1 i) you win a dollar which we
represent it by a1 = $1 and when it is a tail you lose a dollar which we represent
by a2 = $1. I toss the coin 5 times and the following is the outcome.
Figure 1.3: Two sides of a penny represented using bra-vectors.
a1 $1 $1 $1
a2 -$1 -$1
This indicate that three times the outcome is ja1 i and two times it is ja2 i.
Average value: Suppose you are interested in …nding the average money you
won in the game, which we may represent by A; or hAi. This average can be
determined by dividing the total outcome to the total number you toss the coin,
which is given by
1
A = hAi = (3a1 + 2a2 ) : (1.66)
5
I want to express this, more generally, as
2
X
2 2 2
A = hAi = jc1 j a1 + jc2 j a2 = jci j Ai : (1.67)
i=1
where
2 3 2 2
jc1 j = ; jc2 j = (1.68)
5 5
and also it is important to note that
2 2
jc1 j + jc2 j = 1: (1.69)
Let’s de…ne a ket vector j i which represent "the state vector for the coin".
This vector represents all the possible outcomes for any given toss
2
X
j i = c1 ja1 i + c2 ja2 i = ci jai i (1.70)
i=1
and the corresponding bra vector h j

2
X
h j = ha1 j c1 + ha2 j c2 = haj j cj : (1.71)
j=1
Then the bra-ket of "the sate vector of the coin" becomes

2 2
h j i = jc1 j ha1 j a1 i + jc2 j ha2 j a2 i + c1 c2 ha1 j a2 i + c2 c1 ha2 j a1 i : (1.72)
Nothing set of vectors fja1 i ; ja2 ig must form an orthonormal set of vectors,
1; i=j
haj j ai i = ij = : (1.73)
0; i 6= j
in order to …nd
2 2
jc1 j + jc2 j = 1: (1.74)
Therefore for the state vector, describing the state of the coin in this case, must
satisfy the condition
h j i = 1: (1.75)
Using the property of the Kronecker delta, one may write the average value as
2
X 2 X
X 2 2 X
X 2
2
hAi = jci j ai = ci ai cj ij = ci ai cj ij: (1.76)
i=1 i=1 j=1 i=1 j=1
Substituting the relation

ij = haj j ai i ; (1.77)
we have
2 X
X 2 2 X
X 2 2
X 2
X
hAi = ci ai cj haj j ai i = haj j cj ai ci jai i = haj j cj ai ci jai i
i=1 j=1 i=1 j=1 j=1 i=1
(1.78)
so that using
2
X 2
X
Aj i = Ai ci jai i ; h j = haj j cj (1.79)
i=1 j=1
one can write the average value as

2
X 2
hAi = jci j ai = h j A j i : (1.80)
i=1
This is the average value for A which in quantum mechanics commonly know
us expectation value.
Standard deviation: The standard deviation (SD) is a measure that is used
to quantify the amount of variation or dispersion of a set of data values. A low
standard deviation indicates that the data points tend to be close to the average
(the expectation value) of the set, while a high standard deviation indicates
that the data points are spread out over a wider range of values. Generally, the
standard deviation ( A) is determined using the relation
v
rD E uu1 X N
( A) = t
2 2
A= an A : (1.81)
N n=1
For the coin toss game, this becomes

r h i1=2 r 1=2
1 2 2 3 2 2 2
( A) = 3 a1 A + 2 a2 A = a1 A + a2 A
5 5 5
v v
u 2 u 2
uX 2 uX 2
=t =t
2
jci j ai A jci j a2i 2Aai + A2 : (1.82)
i=1 i=1
Once again using the property of the Kronecker delta, one can put the above
expression in the form
v
u 2 2
uX X
( A) = t cj ci ij a2i 2Aai + A2 (1.83)
i=1 j=1
and substituting
ij = haj j ai i (1.84)
the standard deviation becomes

v v
u 2 2 u 2 2
uX X uX X
( A) = t cj ci haj j ai i a2i 2Aai + A2 =t haj j c j a2i 2Aai + A2 ci jai i
i=1 j=1 i=1 j=1
v
u 2 2 2 X
2 2 X
2
uX X X X
=t haj j cj a2i ci jai i 2 haj j cj Aai ci jai i + haj j cj A2 ci jai i:
i=1 j=1 i=1 j=1 i=1 j=1
(1.85)
We recall that A is the average value which is independent of the summation

indices, one may write
2
X2 2
X 2
X 2
X
( A) = 4 haj j cj a2i ci jai i 2A haj j cj ai ci jai i
j=1 i=1 j=1 i=1
31=2
2
X 2
X
+A2 haj j cj ci jai i5 (1.86)
j=1 i=1
Following similar notation we used earlier

6
X 6
X 6
X
Aj i = ai ci jai i ; h j = haj j cj ; and A2 j i = a2i ci jai i (1.87)
i=1 j=1 i=1
one can put the standard deviation in the form

q q
( A) = h j A2 j i 2A h j A j i + A2 h j i = hA2 i 2 A2 + A2
q
1=2 2
= A2 A2 ) ( A) = hA2 i hAi : (1.88)
Note that we have used the relations and notations that we have already shown
earlier
A = hAi = h j A j i ; h j i = 1 (1.89)
and
h j A2 j i = A2 (1.90)
Throwing a dice: A dice has six sides (see Fig.1.4 ). When you throw a
dice the side of the dice facing up (the outcome) will then be any one of these
six sides. Let’s represent these sides using the ket vectors,
8 9
>
> 1 ! ja1 i > >
>
> >
>
>
> 2 ! ja2 i > >
< =
3 ! ja3 i
(1.91)
>
> 4 ! ja4 i > >
>
> >
>
>
> 5 ! ja5 i > >
: ;
6 ! ja6 i
Figure 1.4: A dice.
Figure 1.5: The six possible outcome (state of a dice).

(see Fig.1.4).
You throw the dice and the outcome could be any one of the sides represented
by the ket vector jan i : Let’s assign a price tag, an ; (that the player may be
warded as a winner or loser of the game) corresponding to each outcome jan i ;
where n = 1; 2::6: Suppose we throw the dice a hundred times and the outcome
are found to be 8 9
>
> 16 ! ja1 i ) a1 > >
>
> >
>
> 34 ! ja2 i ) a2 > >
>
< =
15 ! ja3 i ) a3
(1.92)
>
> 5 ! ja4 i ) a4 > >
>
> 6 >
>
>
> ! ja5 i ) a5 > >
: ;
24 ! ja6 i ) a6
Then the average prize that you win, A or the expectation value hAi, can be
expressed as
1
A = hAi = (16a1 + 34a2 + 15a3 + 5a4 + 6a5 + 24a6 ) : (1.93)
100
We may rewrite this in the form
2 2 2 2 2 2
A = hAi = jc1 j a1 + jc2 j a2 + jc3 j a3 + jc4 j a4 + jc5 j a5 + jc6 j a6
6
X 2
) A = hAi = jci j ai ; (1.94)
i=1
where
2 16 2 34 2 15
jc1 j = ; jc2 j = ; jc3 j = ;
100 100 100
2 5 2 6 2 24
jc4 j = ; jc5 j = ; jc6 j = ; (1.95)
100 100 100
and
2 2 2 2 2 2
jc1 j + jc2 j + jc3 j + jc4 j + jc5 j + jc6 j = 1: (1.96)
Suppose we de…ne a ket vector j i which is known as "the state vector of the
dice" which should represent all the possible outcomes for any given throw. This
vector can be written as
6
X
j i = c1 ja1 i + c2 ja2 i + c3 ja3 i + c4 ja4 i + c5 ja5 i + c6 ja6 i = ci jai i (1.97)
i=1
and the corresponding bra vector h j

6
X
h j = ha1 j c1 + ha2 j c2 + ha3 j c3 + ha4 j c4 + ha5 j c5 + ha6 j c6 = haj j cj (1.98)
j=1
For a similar reason we stated in the coin toss, the set of vectors
fja1 i ; ja2 i ; ja3 i ::: ja6 ig

form an orthonormal set of vectors and must satisfy the condition

1; i = j;
haj j ai i = ij = (1.99)
0; i 6= j:
so that one can …nd
2 2 2 2 2 2
jc1 j + jc2 j + jc3 j + jc4 j + jc5 j + jc6 j = 1
) h j i = 1: (1.100)
Following a similar procedure we used in the coin toss, one may write the average
value as
6
X 6 X
X 6 6 X
X 6
2
hAi = jci j ai = ci ai cj ij = ci ai cj ij: (1.101)
i=1 i=1 j=1 i=1 j=1
Substituting the relation

ij = haj j ai i
we have
6 X
X 6 6 X
X 6 6
X 6
X
hAi = ci ai cj hai j aj i = haj j cj ai ci jai i = haj j cj ai ci jai i
i=1 j=1 i=1 j=1 j=1 i=1
(1.102)
so that using
6
X 6
X
Aj i = ai ci jai i ; h j = haj j cj (1.103)
i=1 j=1
one can write the average value as

hAi = h j A j i :
For the standard deviation (SD), we have
16 2 34 2 15 2 5 2
( A) = a1 A + a2 A + a3 A + a4 A
100 100 100 100
1=2
6 2 24 2
+ a5 A + a6 A
100 100
n
2 2 2 2 2 2
= jc1 j a1 A + jc2 j a2 A + jc3 j a3 A
o1=2
2 2 2 2 2 2
+ jc4 j a4 A + jc5 j a5 A + jc6 j a6 A
" 6 #1=2 " 6 #1=2
X 2 2 X 2
= jci j ai A = jci j a2i 2Aai + A2
i=1 i=1
2 31=2
X6 X
6
= 4 cj ci ij a2i 2Aai + A2 5 :
i=1 j=1
which can be put in the form

2 31=2
X6 X
6
( A) = 4 cj ci haj j ai i a2i 2Aai + A2 5
i=1 j=1
2 31=2
X6 X
6 6 X
X 6 6 X
X 6
=4 haj j cj a2i ci jai i 2 haj j cj Aai ci jai i + haj j cj A2 ci jai i5
i=1 j=1 i=1 j=1 i=1 j=1
2
X6 6
X 6
X 6
X
) ( A) = 4 haj j cj a2i ci jai i 2A haj j cj ai ci jai i
j=1 i=1 j=1 i=1
31=2
6
X 6
X
+A2 haj j cj ci jai i5 (1.104)
j=1 i=1
Following a similar notation we used earlier

6
X 6
X 6
X
Aj i = ai ci jai i ; h j = haj j cj ; A2 j i = a2i ci jai i (1.105)
i=1 j=1 i=1
one can put the standard deviation in the form

1=2 1=2
( A) = h j A2 j i 2A h j A j i + A2 h j i = A2 2A2 + A2
q
1=2 2
= A2 A2 ) ( A) = hA2 i hAi ; (1.106)
where we used
A = hAi = h j A j i ; h j i = 1; and h j A2 j i = A2 (1.107)
1.5 Magnetization
Magnetic dipole moment: for a steady current, I; ‡owing in a closed conducting
loop the magnetic dipole moment is given by
Z
~ = I d~a0 = I~a = Ia^
m n;
where ~a = a^
n; a is the area bounded by the conducting loop and n^ is the unit
vector normal to the area.
Torque and Force on a magnetic Dipole: A magnetic dipole experiences a
magnetic force and torque in a magnetic …eld.
Due to the motion of the electron around the nucleus (orbital motion) or
spinning of the electrons (spin motion) there are tiny current loops. In the
macroscopic scale these tiny current loops form a magnetic dipole moment. In
1.5. MAGNETIZATION 21
Figure 1.6: Magnetic moment for rectangular and circular current loop.
Figure 1.7: A magnetic dipole in a region of magnetic …eld.

the …rst case it is orbital magnetic moment and in the later case it is spin mag-
netic moment. In a magnetic materials, with no external magnetic …eld, these
dipole moments are randomly oriented and the net dipole moment in the mate-
rial is zero. However, if external magnetic …eld is applied, due to the resulting
torque, the dipoles align either parallel or antiparallel to the direction of the
external magnetic …eld. According to the alignment of the dipole, magnetic
materials are classi…ed as
Paramagnets: parallel to the external magnetic …eld (due to spin magnetic

moment)
Diamagnets: antiparallel to the external magnetic …eld (due to orbital

magnetic moment)
Ferromagnets: keep their magnetization even after the removal of the

external magnetic …eld
Torque and Force on Magnetic Dipoles: Consider a rectangular current loop

with a magnetic dipole moment, m; ~ pointing in the direction shown below (it
makes an angle from the z axis toward the positive y axis). It is placed in a
uniform magnetic …eld B ~ pointing along the positive z axis. We are interested
in the net force and the torque on this loop.The force on the two slopping sides
Figure 1.8: A rectangular loop carrying a current in a uniform magnetic …eld.
(i.e. the sides with length a) cancel each other. This can be veri…ed using the
right hand rule. The same is true for the other two sides (side with length b)
and the net force is zero on the loop. However, the torque is not zero since the
two forces on the none slopping sides (sides with length b) tends to rotate the
loop in the counterclockwise direction since they do not have the same line of
1.5. MAGNETIZATION 23
action (see Fig. 1.8). The force on the upper side of the loop (side with length
b) is
F~2 = I~l B
~ = Ib^x B y^ = IbB z^ (1.108)
and the corresponding position vector (for center) of this side (i.e. its center)
a a
~r2 = sin y^ + cos z^: (1.109)
2 2
Similarly for the bottom side, the force is
F~1 = IbB z^ (1.110)
and the position vector for its center is

a a
~r1 = sin y^ cos z^: (1.111)
2 2
Then the net torque on the loop can be expressed as
~ = ~r1 F~1 + ~r2
N F~2
~ = a sin y^
)N
a
cos z^ ( IbB z^) +
a a
sin y^ + cos z^ (IbB z^)
2 2 2 2
)N~ = IabB sin x
^ (1.112)
For a rectangular loop of sides a and b and carrying a current I, the magnetic
dipole moment, m;
~ is given by
Z
~ = I d~a0 = (Iab) n
m ^ ) m = Iab
so that the net torque becomes

~ =
N mB sin x ~ =m
^)N ~ ~
B (1.113)
The torque causes a clockwise rotation about the x-axis. This could lead to
a parallel alignment of the dipole moment with the external magnetic …eld. A
material that shows this kind of response to external magnetic …eld is known
as paramagnetic material. Paramagnetism occurs only in atoms or molecules
with odd number of electrons as it is a result of the interaction of the spin
magnetic moment of the electron. If the atoms or molecules are made of even
number of electrons, according to the Pauli exclusion principle (as you recall
from your modern physics class) the electrons form Pair of electrons, due to
Pauli’s exclusion principle, occupying the same energy level must carry opposite
spin which results in opposite magnetic dipole moments. As a result, the net
magnetic moment is zero that lead to zero torque.
In a uniform …eld the net magnetic force on a current loop is zero
I I
F~ = I d~l B ~ =I d~l ~ = 0:
B (1.114)
Figure 1.9: A circular current carrying wire at one end of a solenoid centered
about the axis of the solenoid.
For a none uniform …eld, however, the net force is not zero. Consider a circular
loop placed near the top end of a solenoid shown in Fig. 1.9
Using cylindrical coordinates we may express the magnetic …eld of the solenoid
near top end of the solenoid where the dipole is positioned at can be expressed
as
~ (s; z) = B sin z^ + B cos s^:
B (1.115)
For an in…nitesimal length, d~l; on the dipole (circular loop of radius R carrying
a current I in a counterclockwise direction), we have
d~l = R^
'd' (1.116)
and the net force on the dipole can be determined using

02 1
I Z
F~ = I d~l B ~ = I @ R^ 'd'A (B sin z^ + B cos s^)
0
0 1
Z2 Z2
) F~ = IRB @sin '
^ z^d' + cos '
^ s^d'A : (1.117)
0 0
Noting that
'
^ z^ = s^ = cos '^
x + cos '^
y; '
^ s^ = z^ (1.118)
the net force is found to be
F~ = 2 IRB cos z^: (1.119)

1.6. MAGNETIC MOMENT, ANGULAR MOMENTUM, AND SPIN 25
For an in…nitesimal loop, with dipole moment m, ~

~ in a none uniform …eld B,
using the magnetic energy
U= m ~ B~ (1.120)
one can write the magnetic force exerted on a magnetic dipole as
F~ = OU = O m ~ = O (mx Bx + my By + mz Bz )
~ B (1.121)
For a none uniform magnetic …eld directed along the z-axis, (Bx = By = 0), we
have
F~ = OU = O m ~ B ~ = O (mz Bz ) : (1.122)
If the change in the magnetic …eld with respect to x and y direction is negligible
and the z component of the magnetic …eld does not change in the region, one
can make the approximation
@Bz
F~ = mz z^: (1.123)
@z
Figure 1.10 shows a non–uniform magnetic …eld directed along the z-axis created
Figure 1.10: Magnetic dipoles in a Non-uniform magnetic …eld.
by two magnets. The blue arrow shows the direction of the magnetic force on
two dipoles with oppositely directed magnetic moments.
1.6 Magnetic moment, angular momentum, and

spin
Magnetic moment and orbital angular momentum in an atom: In an atom the
electrons revolve around the nucleus. Let’s consider an electron of charge q and
Figure 1.11: An electron revolving around the nucleus in a circular orbit.
also assume the electron orbit is circular with radius R and period T . (see Fig.
1.11)
In Gaussian units the magnetic moment, m; ~ of a conducting loop carrying
a current, I; is given by
I
m
~ = ~a;
c
where c is the speed of light and ~a is the area.
The magnitude of the electrical current generated, I, due to the orbital
motion of the electron
q
I=
T
using the average orbital speed for the electron
2 R 2 R
v= )T = :
T v
can be expressed as
q qv
I= = :
T 2 R
Due to this current the atom possesses an orbital magnetic dipole moment
Z
I I R2 qR
m~ = d~a0 = z^ = v^
z;
c c 2c
Orbital Angular momentum: we recall that the angular momentum, L, ~ of a

point mass M moving with a velocity ~v in an orbit at a position ~r is given by
~ = M~r
L ~v (1.124)
1.6. MAGNETIC MOMENT, ANGULAR MOMENTUM, AND SPIN 27
for an object with none uniform mass distribution

Z
~
L = (~r ~v ) dM: (1.125)
For the electron the angular momentum can then be expressed as
~
L
~ = me~r
L ~v = me Rv^
z ) v^
z= (1.126)
me R
so that the magnetic moment in terms of the orbital angular momentum of the
electron becomes
qR q ~
m~ = v^
z= L (1.127)
2c 2cme
This relationship between m
~ and L~ is generally true whenever the mass and the
charge coincide in space. One can obtain di¤erent constants of proportionality
by adjusting the charge and mass distribution.
~ of a particle is
Magnetic moment due to Intrinsic spin: Intrinsic spin, S;
given by
gq ~
m~ = S
2cme
where the value of the constant g is
8
< 2:00 electron
g= 5:58 proton
:
3:82 neutron
Chapter 2
Stern-Gerlach Experiments
Classically, the magnetic moment due to orbital motion which is proportional

to the orbital angular momentum
qR q ~
m
~ = v^
z= L (2.1)
2c 2cme
As shown in Fig.2.1 for a magnetic dipole interacting with a magnetic …eld, if
Figure 2.1: A classical magnetic dipole.
one measures the z-component of the magnetic moment, one …nds
mz = jmj
~ cos ( ) ) jmj
~ mz jmj
~ :
29
30 CHAPTER 2. STERN-GERLACH EXPERIMENTS
This shows that the z-component of the magnetic moment takes any value be-
tween jmj ~ and jmj~ (i.e. it takes a continuum values). Similar magnetic inter-
action takes place due to the spin magnetic moment when a spin-1/2 particle
passes through a region where there is a magnetic …eld and one may expect
a similar result for the z-component of the spin magnetic moment. But the
Stern–Gerlach experiment showed contrary to classical prediction.
The Stern–Gerlach experiment involves sending a beam of particles through
an inhomogeneous magnetic …eld and observing their de‡ection. The results
show that particles possess an intrinsic angular momentum that is closely anal-
ogous to the angular momentum of a classically spinning object, but that takes
only certain quantized values. Another important result is that only one com-
ponent of a particle’s spin can be measured at one time, meaning that the mea-
surement of the spin along the z-axis destroys information about a particle’s
spin along the x and y axis.
History of the Stern–Gerlach experiment [From Wikipedia]: The Stern–
Gerlach experiment was performed in Frankfurt, Germany in 1922 by Otto Stern
and Walther Gerlach. At the time, Stern was an assistant to Max Born at the
University of Frankfurt’s Institute for Theoretical Physics, and Gerlach was an
assistant at the same university’s Institute for Experimental Physics.
Figure 2.2: Stern–Gerlach experiment
At the time of the experiment, the most prevalent model for describing the
atom was the Bohr model, which described electrons as going around the posi-
tively charged nucleus only in certain discrete atomic orbitals or energy levels.
31
Since the electron was quantized to be only in certain positions in space, the
separation into distinct orbits was referred to as space quantization. The Stern–
Gerlach experiment was meant to test the Bohr–Sommerfeld hypothesis that the
direction of the angular momentum of a silver atom is quantized. The Stern–
Gerlach experiment was performed several years before Uhlenbeck and Goudsmit
formulated their hypothesis of the existence of the electron spin. Even though
the result of the Stern-Gerlach experiment has later turned out to be in agree-
ment with the predictions of quantum mechanics for a spin- 1/ 2 particle, the
experiment should be seen as a corroboration of the Bohr–Sommerfeld theory.
The schematic diagram of the original Stern-Gerlach experiment is shown in
Fig. 2.3
Figure 2.3: The Stern-Gerlach experiment.
We recall the direction in which the inhomogeneous magnetic …eld is large

is the z direction,
@Bz
F~z ' mz z^:
@z
Classically, mz = jmj
~ cos ; which takes continuum values between m and m:
But the SG experimental result con…rmed that mz takes on only two values
corresponding to the values ~=2; where
27 16
~ = h=2 = 1:055 10 erg:s = 6:582 10 eV:s
h is Planck’s constant.
Silver atom has 47 electron and a nucleus. The 46 electrons have zero total
orbital and total spin angular momentum. The 47th electron has zero orbital
angular momentum but nonzero spin angular momentum. The spin due to the
nucleus has negligible contribution since the mass, M; is big as compared to the
mass of the electron
gq ~
m
~ = S ' 0 for the nucleus.
2M c
Therefore, the measured magnetic moment must be due to the spin magnetic
moment of the electron.
2.1 Virtual experiment by SG device

Let’s perform three virtual (thought) experiments using SG device as shown in
the …gure below.
Virtual Experiment 1: Particles with random spin enters into an SGz
device (i.e. the inhomogeneous magnetic …eld parallel to the z axis). The
particle exiting this device according to the real SG experiment should have a
spin Sz = +~=2 or ~=2: We represent the spin state of a particle with spin
+~=2 by the ket vector j+Zi and with spin ~=2 by j Zi. Now let’s send the
particles emerging from the SGz device in a spin state j+Zi into a second SGz
device: The particle emerging from the second SGz device are all have a spin
Sz = +~=2 (i.e. are in state j+Zi).
100% Sz = +~=2 ( in state j+Zi) (2.2)
This indicate that
Figure 2.4: Stern–Gerlach Virtual experiment 1. [From PHET Simulation web-

site, University of Colorado at Boulevard, Colorado].
2
jh+Z j+Zij = 1 (2.3)
and exiting in state j Xi is
2
jh Z j+Zij = 0 (2.4)
2.1. VIRTUAL EXPERIMENT BY SG DEVICE 33
Virtual Experiment 2: Particles with random spin enters into an SGz device.
The particles emerging in a spin state j+Zi entered into a second SG device
with the inhomogeneous magnetic …eld parallel to the x axis: We name this
device SGx. In this experiment half of the particles emerging from will have a
Figure 2.5: Stern–Gerlach Virtual experiment 2.
spin of Sx = +~=2 and the other half a spin Sx = ~=2: The spin state of these
particles can be represented as j+Xi and j Xi ; respectively.
50% Sx = +~=2 ( in state j+Xi)

(2.5)
50% Sx = ~=2 ( in state j Xi)
The result of this experiment indicates the probability for a particle in state
j+Zi exiting SGx in a state j+Xi, is given by
2 1
jh+X j+Zij = (2.6)
2
and exiting in state j Xi is
2 1
jh X j+Zij = (2.7)
2
so that the probabilities for each case becomes
2 2
jh+X j+Zij + jh X j+Zij = 1 (2.8)
Virtual Experiment 3: Particles with random spin enters into an SGz device.
The particles emerging in a spin state j+Zi entered into a second SGx. The
particles emerging from SGx in a spin state j+Xi enters into a third SG device
with the inhomogeneous magnetic …eld parallel to the z axis (SGz). Half of the
Figure 2.6: Stern–Gerlach Virtual experiment 3.
particle emerging will be in a spin state j+Zi and the other half in a spin state
j+Zi :
50% Sz = +~=2 ( in state j+Zi)

(2.9)
50% Sz = ~=2 ( in state j Zi)
This also indicates the probability for a particle in state j+xi exiting the second
SGz in a state j+Zi, is given by
2 1
jh+Z j+Xij = (2.10)
2
and exiting in state j Zi is
2 1
jh Z j+Xij = (2.11)
2
and the total probability becomes
2 2
jh+Z j+Xij + jh Z j+Xij = 1 (2.12)
or
2 2
jc+ j + jc j = 1 (2.13)
where
c+ = h+Z j+Xi ) c+ = [h+Z j+Xi] = h+X j+Zi

c = h Z j+Xi ) c = [h Z j+Xi] = h+X j Zi (2.14)
Next we shall see how these probabilities related to the state vector for the spin-
1/2 particle. Note that if we consider starting from the state when the particles
2.2. THE SPIN QUANTUM STATE VECTOR 35
enter the …rst SGz, the probability of the particles emerging from the second
SGz device in state j+Zi
1
h+X j+Zi h+Z j+Xi = (2.15)
4
and in state j Zi
1
h+X j+Zi h Z j+Xi = (2.16)
4
We will revisit these results in Experiment 4
2.2 The spin quantum state vector

In experiment 3, the measurement of the particles spin exiting the second SGz
showed that 50% of the particles are in j+Zi state and the other 50% are in
j Zi state. This suggests that before we conduct the measurement, a spin-1/2
particle could either be in the state j+Zi or j Zi : Therefore, the state of the
particle entering into the second SGz and interacting with the magnetic …eld,
generally, must be a linear superposition of the states j+Zi and j Zi : This
state represented by the ket vector, j i ;
j+Xi = j i = c+ j+Zi + c j Zi ; (2.17)
where c+ and c are the probability amplitudes which are generally complex.
These probability amplitudes are determined using the bra vectors h+Zj and
h Zj :
h+Zj i = c+ h+Zj +Zi + c h+Zj Zi = c+

h Zj i = c+ h Zj +Zi + c h Zj Zi = c (2.18)
It is important to note that a particle known to be in the state j Zi can not

be in the state h+Zj at the same time, as we already saw in Experiment 1
h+Zj Zi = h+Zj +Zi = 0: (2.19)
This means if you take a measurement for the z-component of the spin Sz on a
spin-1/2 particle you can not get ~=2 and ~=2 at the same time. We also need
to note that
h+Z j+Zi = 1; h Z j Zi = 1 (2.20)
as once the particle is known to be in a state j+Zi it always be in that state

(Virtual experiment 1). Using the expressions for the probability amplitudes c+
and c , we can write the state vector
j i = h+Z j i j+Zi + h Z j i j Zi (2.21)

Taking into consideration the properties in bra-ket formulation, one can rewrite
this expression in the form
j i = j+Zi h+Z j i + j Zi h Z j i = (j+Zi h+Zj + j Zi h Zj) j i
) j i = I^ j i = j i (2.22)
where
I^ = j+Zi h+Zj + j Zi h Zj : (2.23)
^
For now we call I, the identity operator according to what we know from theo-
retical physics.
If the particle is in a state j i, the probability of …nding the particle in this
state is one. This means
h j i = 1 ) c+ h+Zj + c h Zj (c+ j+Zi + c j Zi) = 1
) c+ c+ h+Z j+Zi + c+ c h+Z j Zi + c c+ h Z j+Zi + c c h Z j Zi = 1
2 2
) c+ c+ + c c = 1 ) jc+ j + jc j = 1 (2.24)
Since when we take the measurement of Sz using the second SGz device we
found 50% Sz = ~=2 and 50% Sz = ~=2. Thus
2 2 1 p p 1
jc+ j = jc j = ) jc+ j = c+ c+ = jc j = c c = p (2.25)
2 2
Since c+ and c are, in general, complex we must write
1 1
c+ = jc+ j ei +
; c = jc j ei ) c+ = p ei +
; c = p ei : (2.26)
2 2
Therefore, the state vector j i can be written as
1 1
j i = p ei +
j+Zi + p ei j Zi (2.27)
2 2
Example 1 Find the average value and the standard deviation (uncertainty)
for the measurement of the z-component of the spin for the particles in
Experiment 3:
Solution: The state vector
1 1
j i = p ei +
j+Zi + p ei j Zi (2.28)
2 2
tells us the probability amplitudes are
1 1
c+ = p ei +
; c = p ei : (2.29)
2 2
~ ~
for a spin value of Sz = 2 and Sz = 2; respectively. Then the average
value
2 2 1 ~ 1 ~
hSz i = jc+ j S+ + jc j S = + =0 (2.30)
2 2 2 2
2
The standard deviation in the measurement of Sz (( Sz ) ):
q
2
( Sz ) = hSz2 i hSz i
The average value of Sz2 can be calculated using the probability amplitudes
and the value for Sz2
2 2
2 ~ 2 ~ 1 ~2 1 ~2 ~2
Sz2 = jc+ j + jc j = + =
2 2 2 4 2 4 4
Thus the standard deviation (the uncertainty) becomes
q r
2 2 ~2 ~
( Sz ) = hSz i hSz i = ) Sz = :
4 2
Example 2 Find the average value and the standard deviation (uncertainty)
for the measurement of the z-component of the spin for the particles de-
scribed by the spin state vector
p
1 3
j i = j+Zi i j Zi (2.31)
2 2
Solution: The state vector
p
1 3
j i= j+Zi i j Zi (2.32)
2 2
tells us the probability amplitudes are
p
1 3 i
c+ = ; c = i e : (2.33)
2 2
~ ~
for a spin value of Sz = 2 and Sz = 2; respectively. Then the average
value
2 2 1 ~ 3 ~ ~
hSz i = jc+ j S+ + jc j S = + = (2.34)
4 2 4 2 4
2
The standard deviation in the measurement of Sz (( Sz ) ):
q
2
( Sz ) = hSz2 i hSz i
The average value of Sz2 can be calculated using the probability amplitudes
and the value for Sz2
2 2
2 ~ 2 ~ 1 ~2 3 ~2 ~2
Sz2 = jc+ j + jc j = + =
2 2 4 4 4 4 4
Thus the standard deviation (the uncertainty) becomes
q r r p
2 2 ~2 ~2 3~2 3~
( Sz ) = hSz i hSz i = = ) Sz = :
4 16 16 4
Modi…ed SG device: Suppose we modi…ed the SG device as shown in

Fig.??. The outer two device are exactly the same SG device. In between these
two devices we have two another SG devices with the polarities of the magnet
switched and the length is twice the length of the other two SG device.
Figure 2.7: Modi…ed SG device. [Modi…ed from diagram in The Feynman lec-
tures]
Virtual Experiment 4: We replace the SGx in experiment 3 by the modi-

…ed SGx as shown in Fig.2.8. The outcome of the experiment is that the proba-
bility of the particles emerging from the second SGz device with spin Sz = ~=2
is found to be zero. All the particles emerging from the second SGz device has
a spin Sz = ~=2:
This means in terms of the probability amplitudes what the experiment
shows is that
h+X j+Zi h+Z j+Xi + h+X j+Zi h+Z j Xi = 1;
h+X j+Zi h Z j+Xi + h+X j+Zi h Z j Xi = 0:
On the other hand in Experiment 3 these probabilities are found to be
1
h+X j+Zi h+Z j+Xi = (2.35)
4
and in state j Zi
1
h+X j+Zi h Z j+Xi = (2.36)
4
The results in Experiment 3 and Experiment 4 shows that there is some amlitude
interference that can be explained only by quantum mechanics...
Figure 2.8: Experiment 4 where SGx device is replaced by Modi…ed SGx device
with both states (j+Xi and j Xi)open.
Figure 2.9: Experiment 3 with modi…ed SGx apparatus with j+Xi open and
j Xi blocked.
Virtual Experiment 5: Replace SGz in experiment 3 by SGy in which

the gradient in the magnetic …eld is in the y direction. If we measure Sy for
the particles exiting SGy we …nd 50% of the particle spin up (i.e. in the state
j+Y i) and 50% in spin down (i.e. in state j Y i).
In experiment 3 if we replace SGx by SGy and measure Sy using SGz, the

probability distribution is going to be still the same (50% of the particles in state
j+Zi with Sz = ~=2 and 50% in state j Zi with Sz = ~=2). This indicates
the state of the particles exiting SGy with a spin up state j+Y i in experiment
5 are superposition of the j+Zi and j Zi which we write as
j+Y i = d+ j+Zi + d j Zi ; (2.37)
where d+ and d are the probability amplitudes and complex in general like c+
and c : Noting that particles in j+Y i state to be found in this same state is
100%; we have
2
jh+Y j+Y ij = 1 ) d+ d+ + d d = 1: (2.38)
Since when we make the measurement for Sz ; the outcome would be 50% Sz =
~=2 and 50% Sz = ~=2; we may write
1 1 1
d+ = p ei ; d = p ei ) j+Y i = p ei + j+Zi + ei
+
j Zi
2 2 2
i +
e
) j+Y i = p j+Zi + ei( +)
j Zi : (2.39)
2
or introducing = + we may write
ei +
j+Y i = p j+Zi + ei j Zi : (2.40)
2
We already have seen that the particles exiting SGx in the state j+Xi and
entering SGy are a superposition of j+Zi and j Zi given by
1 1
j+Xi = p ei +
j+Zi + p ei j Zi (2.41)
2 2
ei +
) j+Xi = p j+Zi + ei j Zi : (2.42)
2
in a similar manner one can write this state vector as
ei +
j+Xi = p j+Zi + ei j Zi ; (2.43)
2
where = +:
Condition for 50% of the particles to be in j+Y i: We know that if we make
a measurement for Sy we …nd 50% Sy = ~=2. This means
2 1
jh+Y j+Xij = (2.44)
2
Using the the expression for j+Xi
ei +
j+Xi = p j+Zi + ei j Zi (2.45)
2
and the complex conjugate of j+Y i
ei +
j+Y i = p j+Zi + ei j Zi (2.46)
2
given by
ei + i
h+Y j = p h+Zj + e h Zj (2.47)
2
we may write
2
2 ei + i ei + 1
jh+Y j+Xij = p h+Zj + e h Zj p j+Zi + ei j Zi =
2 2 2
i 2
) h+Z j+Zi + e h Z j+Zi + ei h+Z j Zi + ei( )
h Z j Zi = 2:
(2.48)
Recalling that h+Z j+Zi = h Z j Zi = 1 and h Z j+Zi = h+Z j Zi = 0 so

that
2
1 + ei( )
= 2 ) 1 + ei( )
1+e i( )
=2
1 + ei( )
+e i( )
+ 1 = 2 ) cos ( ) + i sin ( ) + cos ( )
i sin ( ) = 0 ) cos ( )=0) = (2.49)
2
Therefore, the above result shows the probability of the particles exiting SGy
in state j+Y i to be 50% depends on the di¤erence between the relative phase
and of the state j+Xi and the state j+Y i rather than the individual phases
of the + ; + , and : From this result we also learn that the fact that
the probability amplitudes in a superposed states are in general complex is very
crucial. It also shows that in quantum mechanics the phase of the probability
amplitudes plays an important role.
Since the probability depends on the relative phases and ;we can drop
+ ; + in the expressions for j+Xi and j+Y i,
1 1
j+Xi = p j+Zi + ei j Zi ; j+Y i = p j+Zi + ei j Zi : (2.50)
2 2
If one chooses = 0; we have
= ) = (2.51)
2 2
so that j+Xi and j+Y i becomes
1 1
j+Xi = p (j+Zi + j Zi) ; j+Y i = p (j+Zi + i j Zi) (2.52)
2 2
1 1
) j Xi = p (j+Zi j Zi) ; j Y i = p (j+Zi i j Zi)(2.53)
2 2
for a right handed coordinate system. On the other hand for a left handed
coordinate system, for = 0
= ) = (2.54)
2 2
we …nd
1
j+Y i = p (j+Zi i j Zi) = j Y i (2.55)
2
As shown in Fig. 2.11 below what is down in the right coordinate system is up
Figure 2.10: Right and left coordinate systems.
in the left coordinate system and vise versa.
Example 3 A spin-1/2 particle is in the state

p
1 3
j i = j+Zi + i j Zi (2.56)
2 2
(a) What are the probability that a measurement of Sy yields +~=2?

(b) What are the probability amplitude that a measurement of Sy yields ~=2?
(c) What is the expectation values for hSy i ; Sy2 ; and the uncertainties.
Figure 2.11:
Solution:
(a) The state vector p
1 3
j i = j+Zi + i j Zi (2.57)
2 2
is given in the Sz basis. This state can also be expressed in Sy basis states
as we shall see in the next chapter. But for now let say it is given by
p
1 3
j i = j+Zi + i j Zi = c+ j+Y i + c j Y i (2.58)
2 2
so that the probability amplitude, c+ ; of a measurement of Sy yields +~=2
can be expressed as
p
1 3
h+Y j i = c+ h+Y j+Y i + c h+Y j Y i = h+Y j +Zi + i h+Y j Zi
p 2 2
1 3
) c+ = h+Y j +Zi + i h+Y j Zi : (2.59)
2 2
Now using the basis vectors for Sy
1 1
j+Y i = p (j+Zi + i j Zi) ; ) h+Y j = p (h+Zj i h Zj) (2.60)
2 2
we have
1 1
h+Y j +Zi = p ; h+Y j Zi = i p (2.61)
2 2
so that the probability amplitude becomes
p
1 3
c+ = p + p = 0:97 (2.62)
2 2 2 2
and the probability of the measurement for Sy yields +~=2
2
P+ = jc+ j = 0:93 (2.63)
(b) Following a similar procedure one can write

p
1 3
c = h Y j +Zi + i h Y j Zi (2.64)
2 2
so that using
1 1
j Y i = p (j+Zi i j Zi) ; ) h Y j = p (h+Zj + i h Zj) (2.65)
2 2
one …nds
1 1
h Y j +Zi = p ; h Y j Zi = i p (2.66)
2 2
and the probability amplitude
p
1 3
c = p p = 0:26: (2.67)
2 2 2 2
Just for checking our result, for the probability of the measurement for Sy
yields ~=2; we …nd
2
P = jc j = 0:07 (2.68)
so that
2 2
P+ + P = jc+ j + jc j = 1 (2.69)
as one should expect.
(c) Once we …nd the probabilities, to …nd the expectation values for hSy i and
Sy2 ; we can use
2 ~ 2 ~ ~ ~
hSy i = jc+ j + jc j = 0:93 + 0:07 = 0:43~
2 2 2 2
2
) hSy i = 0:185 (2.70)
2 2
2 ~ 2 ~ ~2 ~2
Sy2 = jc+ j + jc j = 0:93 + 0:07
2 2 4 4
) Sy2 = 0:25~ (2.71)
and the uncertainties,

q p
2
( Sy ) = Sy2 hSy i = 0:065~2 = 0:255~: (2.72)
2.3 Generalization for N-states system

Consider a physical observable, A; (like the spin) measurement of which can take
values a1 ; a2 ; a3 :::aN when the system is in a basis state ja1 i ; ja2 i ;
ja3 i ::: jaN i ; respectively.
2.3. GENERALIZATION FOR N-STATES SYSTEM 45
1. The state vector: A general quantum state j i for the system can be written
as linear superposition of the basis states
ja1 i ; ja2 i ; ja3 i :::
X
j i = c1 ja1 i + c2 ja2 i + c3 ja3 i ::: = cn jan i (2.73)
n=1
and the corresponding bra-vector h j

X
h j = c1 ha1 j + c2 ha2 j + c3 ha3 j ::: = cn han j : (2.74)
n=1
The complex number cn given by
cn = han j i (2.75)
is the probability amplitude to obtain, an ; when a measurement of the

observable A is made for the system in a state j i :
The basis state vectors, ja1 i ; ja2 i ; ja3 i ::: form an orthonormal set of vectors,
1 n=m
han jam i = (2.76)
0 n 6= m
Physically this means that for a system in a state jam i if you make a
measurement for the observable A you always …nd a value am : There is
no way that you would …nd an 6= am :
A jam i = am jam i
If an arbitrary vector j i can be expressed as a linear superposition of the

orthonormal basis set of vectors jan i as
X
n
then the vectors jan i are said to be a complete set of vectors and satisfy
the completeness relation
X
jan i han j = 1: (2.78)
n
Proof: Using the probability amplitudes cn given by
cn = han j i (2.79)
we can write
X
n
as X
j i= han j i jan i : (2.81)
n=1
Since cn = han j i is just a complex number and we can write it in front

of jan i
X X
j i= jan i han j i = (jan i han j) j i : (2.82)
n n
For the above equation to be true we must have

X
jan i han j = 1: (2.83)
n
The completeness relation is a very powerful relation. For example, from

the bra vector
X
h j = c1 ha1 j + c2 ha2 j + c3 ha3 j ::: = cm ham j ; (2.84)
m
using the completeness relation we can show that

X X X X
h j jan i han j = cm ham j jan i han j = cm ham jan i han j
n m n m;n
X X X
= cm mn han j ) h jan i han j = cn han j
m;n n n
) cn = h jan i (2.85)
2. For any normalized state vector j i

X
n
we must have
X X X
h j i = cm ham j cn jan i = cn cm ham jan i = 1
m n m;n
X X X 2
) cn cm mn = cn cn = jcn j = 1: (2.87)
m;n n n
3. The average value of the observable A (commonly known as expectation

value) denoted by hAi for a system in a state j i is given by
hAi = h j A j i (2.88)
can be expressed as X 2
hAi = jcn j an : (2.89)
n
Proof: Using
X X
j i= cn jan i and h j = cm ham j (2.90)
n m
we can express the average value as

X X X
hAi = cm ham j A cn jan i = cn cm ham j A jan i (2.91)
m n n;m
We note that han j A jan i is the expectation value of the observable A when
the system is in a state jan i : If the system is in the basis state jan i, when
we take the measurement for A for such state we always …nd that the
value is an : Therefore we can say that
ham j A jan i = mn an : (2.92)
Substituting this in the above expression we …nd

X X 2
hAi = cn cm mn an = jcn j an (2.93)
n;m n
4. For the same observable A the expectation value for A2 ,

X 2
A2 = jcn j a2n (2.94)
n
Proof : The expectation value for A2 is given by
A2 = h j A2 j i (2.95)
which can be expressed as

X X X
A2 = cm ham j A2 cn jan i = cn cm ham j A2 jan i
m n m;n
X
2
) A = cn cm ham j AA jan i (2.96)
m;n
We know that the basis state vectors form a complete set and satisfy the
completeness relation X
jak i hak j = 1: (2.97)
k
We can insert it in between A and A in the expression for A2 above

X X X
A2 = cn cm ham j A jak i hak j A jan i = cn cm ham j A jak i hak j A jan i
m;n k m;k;n
(2.98)
Following the same argument given above we have

X X
A2 = cn cm mk ak kn an = cn cn nk ak kn an
m;k;n k;n
X X 2
) A2 = cn cn nn an nn an = jcn j a2n (2.99)
n n
Example 4 Consider a beam of spin-1 particles incident on an SG apparatus.

The measurement of the spin, Sz ; for spin-1 particles can take values
+~; ~; or 0: Suppose the spin state of such particles is described by the
state vector
r r
1 1 3 1
j i = p j+1i + j 1i + i j0i ; (2.100)
2 2 2 2 2
where j+1i ; j 1i ; and j0i are Sz basis state vectors for spin-1 particles.
(a) What are the probabilities that a measurement of Sz yields +~; ~; and 0?
(b) What are the expectation values for hSz i ; Sz2 ; and the uncertainties.
Solution:
(a) We note that the probability amplitudes can easily be determined using
r r
1 1 3 1
c+1 = h+1j i = p h+1 j+1i + h+1 j 1i + i h+1 j0i
2 2 2 2 2
1
) c+1 = p ;
2 2
r r
1 1 3 1
c 1 = h 1j i = p h 1 j+1i + h 1 j 1i + i h 1 j0i
2 2 2 2 2
r
1 3
) c 1= ;
2 2
r r
1 1 3 1
c0 = h0j i = p h0 j+1i + h0 j 1i + i h0 j0i
2 2 2 2 2
r
1
) c0 = i : (2.101)
2
so that one …nd for the probabilities
2 1 2
P+1 = jc+1 j = jh+1j ij = ;
8
2 2 3
P 1 = jc 1 j = jh 1j ij = ;
8
2 2 1
P0 = jc0 j = jh0j ij = : (2.102)
2
Note that
P+1 + P 1 + P0 = 1 (2.103)
(b) For the expectation values for hSz i ; Sz2
2 2 2 1 3 1
hSz i = jc+1 j ~ + jc 1j ( ~) + jc0 j 0 = ~ ~= ~
8 8 4
2
) hSy i = 0:185 (2.104)
2 2 2 2 1 2 3 2 1
Sy2 = jc+1 j ~2 + jc 1j ( ~) + jc0 j 02 = ~ + ~ = ~
8 8 2
) Sy2 = 0:25~ (2.105)
and the uncertainties,

s
q
2 1 1
( Sy ) = Sy2 hSy i = ~2 = 0:66~: (2.106)
2 16
This example shows what we were introduced to a two state system can
also be applied to multi-state system.
Chapter 3
Rotation of Basis States

and Matrix Mechanics
3.1 Matrix representation of the state vector

Any normalized state vector j i which can be expressed as a linear superposition
of the basis vectors jan i as
X
j i= cn jan i (3.1)
n=0
can be expressed using a column matrix as

0 1
c1
B c2 C
B C
B c3 C
j i=BB
C
C (3.2)
B C
@ A
The corresponding bra vector is represented by a row matrix given by

h j= c1 c2 c3 (3.3)
The row vector that represents the bra is a complex conjugate and transpose of
the column vector that represents the corresponding ket vector. This means
y
h j = [j i] (3.4)
The dagger symbol mean conjugate and transpose.
Example 1 Consider a spin- 21 particles in the SG experiments. The state vec-
tor for these particles in terms of the basis states vectors for Sz is given
by
j i = c+ jZi + c j Zi : (3.5)
Find the matrix representation of the basis vectors.
51
52CHAPTER 3. ROTATION OF BASIS STATES AND MATRIX MECHANICS
Solution: The corresponding matrix representation for the state vector is given
by
c+ 1 0
j i= = c+ +c : (3.6)
c 0 1
There follows that for jZi
1
jZi = (3.7)
0
and j Zi
0
j Zi = : (3.8)
1
Example 2 Find the matrix representation of the ket vector
1
j+Xi = p (j+Zi + j Zi) (3.9)
2
and determine j Xi using the matrix representation of the Sz basis from

the orthonormality condition for the basis state vectors.
Solution: Noting that
1 1 1 0 1 1
j+Xi = p (j+Zi + j Zi) = p + =p
2 2 0 1 2 1
(3.10)
with a corresponding bra vector
1
h+Xj = p 1 1 : (3.11)
2
Using the completeness relation for the Sz basis, we may write
j Xi = (j+Zi h+Zj + j Zi h Zj) j Xi = j+Zi h+Zj Xi

+ j Zi h Zj Xi ) j Xi = j+Zi c0+ + j Zi c = 0
c0+ 0
j+Zi + c j (3.12)
Zi ;
where
c0+ = h+Zj Xi ; c0 = h Zj Xi : (3.13)
The corresponding matrix in this basis can then be expressed as
c0+
j Xi = (3.14)
c0
with a corresponding bra vector
h Xj = c0+ c0 : (3.15)
3.2. ROTATION OPERATORS 53
Taking into consideration that a spin- 12 particle in a state j+Xi can not
be found in a state j Xi ; one may write
1 1 1
h Xj +Xi = c0+ c0 p = 0 ) p c0+ + c0 =0
2 1 2
) c0+ = c0 ) c0+ = c0 ) c0+ c0+ = c0 c0 (3.16)
From the normalization conditions, we have
c0+
h Xj Xi = 1 ) c0+ c0 = 1; ) c0+ c0+ + c0 c0 = 1; (3.17)
c0
so that using the result

c0+ c0+ = c0 c0 ;
we …nd
1
2c0+ c0+ = 2c0 c0 = 1 ) c0+ = c0 =p : (3.18)
2
Noting that the complex variables can be expressed as
0 0
c0+ = c0+ ei + ; c0 = c0 ei (3.19)
one may write

1 0 1 0
c0+ = p ei + ; c0 = p ei (3.20)
2 2
so that
0 0 0
c0+ = c0 ) e i + = ei = e i( )
0 0 0 0
) + = + ) + = : (3.21)
0
Therefore, for + = 0, one can write the state vector j Xi as
1 1
j Xi = p : (3.22)
2 1
Homework 1 Find the matrix representation of the ket vector

1
j+Y i = p (j+Zi + i j Zi) (3.23)
2
and determine j Y i using the matrix representation of the Sz basis from
the orthonormality condition for the basis state vectors.
3.2 Rotation Operators

In chapter one we have introduced to coordinate rotation in terms of Dirac no-
tation. The SG apparatus that we saw in the previous chapter can be described
Figure 3.1: Rotation in 2D Hilber space.
in terms of some rotation operation in some coordinate system in some space

which normally called Hilbert space, in quantum mechanics. To this end let’s
consider a two-dimensional Hilbert space de…ned by the orthonormal basis vec-
tors j+Zi and j Zi ;as shown in Fig.3.1 We do some rotation operation on this
coordinate system that we may represent by R ^ ('j) : Here j included to show
that rotation is about the y axis. We note that from Fig. 3.1
^ ('j) j+Zi = j+Xi ; R

R ^ ('j) j Zi = j Xi
For ' = =4;this operation transforms the basis vectors j+Zi and j Zi into a
new set of basis vectors j+Xi and j Xi :Now we go back to virtual Experiment
3 where spin-1/2 particles in state j+Zi passes through an SGx apparatus that
transforms the state of the particles to j+Xi or j Xi : In this experiment the
measurement of the particles in j+Xi by an SGz apparatus showed that these
particles indeed are in j+Zi or j Zi state with equal probability. Mathemat-
ically, this can then be represented that the SGx does the rotation operation
that can be represented by a rotation operator R^ j acting on the particles in
4
^
the state j+Zi followed by another rotation of R 4 j by the second SGz device
transforming into j+Zi or j Zi state with equal probability. This shows that a
rotation angle required for transforming the particles in the state j+Zi to j+Xi
must then be 2
^
R ^
j =R ^
j R j
2 4 4
in the coordinate space. Thus we can write
^ 1 1
R j j+Zi = j+Xi = p j+Zi + p j Zi (3.24)
2 2 2
similarly
^ 1 1
R j j Zi = j Xi = p j+Zi p j Zi (3.25)
2 2 2
Note that operators act only on ket vectors.
Example 3 Find the rotated state for
j i = c+ j+Zi + c j Zi (3.26)
^
if it is operated by R 2j :
Solution:
^
R ^
j j i=R ^
j (c+ j+Zi + c j Zi) = c+ R j j+Zi
2 2 2
^
+c R j j Zi = c+ j+Xi + c j Xi (3.27)
2
^ j is
Adjoint operator : The adjoint operator to the rotation operator R 4
denoted by R^ y j which rotates the bra vector h+Zj to the bra vector h+Xj
4
and satis…es the condition
^y
R ^
j R j = 1: (3.28)
2 2
This can be shown as
j+Xi = ^
R ^y
j j+Zi ; h+Xj = h+Zj R j
2 2
) ^y
h+Xj +Xi = h+Zj R ^
j R j j+Zi (3.29)
2 2
In order to …nd a normalized rotated state j+Xi ;from an already normalized
states j+Zi and j Zi ;we must have
^y
h+Zj R ^
j R ^y
j j+Zi = 1 , R ^
j R j =I (3.30)
2 2 2 2
^ that satis…es the condition
Unitary operator : an operator U
^ yU
U ^ =U
Û^y = 1 (3.31)
like the rotation operator.

Hermitian operators: In experiment three the spin-1/2 particles state is
rotated from j+Zi into j+Xi by the SGx and SGz device which described by
the equation
^ 1 1
R j j+Zi = j+Xi = p j+Zi p j Zi (3.32)
2 2 2
In a similar manner one can rotate the state j+Xi into j+Y i, making successive
rotations about the z axis (Virtual Experiment 5)then we may write the rotation
operator as R^ k so that one can write
2
^ 1
R k j+Xi = j+Y i = p (j+Zi + i j Zi) (3.33)
2 2
Suppose we do this rotation instead of doing at once, let’s do it by rotating

^ (d'k). Let’s express this
an in…nitesimal angle d' using a rotation operator R
^
rotation operator in terms of a new operator Jz as
^ (d'k) = 1 i ^
R Jz d'; (3.34)
~
where J^z is an operator that does rotation about the z-axis. If there is no
rotation, that means d' ! 0; then R ^ (d'k) must do nothing on the state.
^
Hence as d' ! 0, the operator R (d'k) must be 1 and that is why we have 1 in
the above expression. The corresponding adjoint operator can then be written
as
y y
^ y (d'k) = i ^ i ^ i ^y
R 1 Jz d' =1 Jz d' = 1 J d'
~ ~ ~ z
^ y (d'k) = 1 + i J^y d':
)R (3.35)
~ z
^ (d'k) must satisfy the condition
Since the adjoint operator of R
^ y ('k) R
R ^ ('k) = I (3.36)
we must have
i ^y i ^
1+ J d' 1 Jz d' = I
~ z ~
i ^ i 1 ^y ^ 2
1 Jz d' + J^zy d' + J Jz (d') = 1
~ ~ ~2 z
i ^y 1 ^y ^ 2
J J^z d' + J Jz (d') = 0 (3.37)
~ z ~2 z
2
Since one can make d' arbitrarily small, (d') ' 0. Therefore
i ^y
J J^z d' = 0 ) J^z = J^zy (3.38)
~ z
An operator that is the same as its adjoint operator (i.e. J^z = J^zy ) is called a
Hermitian operator. Nothing that for a given angle ' we can write
'
d' = lim (3.39)
N !1 N
we can write the rotation operator as

N
Y N
^ ('k) = lim ^ (d'k) = lim i ^ ' iJ^z '
R R 1 Jz =e ~ (3.40)
N !1
n=1
N !1 ~ N
Eigenstates and Eigenvalues: Suppose a particle is in the state j n i and you

^ This operator would not change the state vector. But it
act the operator A:
may add a multiplying factor some constant an : Which means
A^ j ni = an j ni
Then the state j ni is called an Eigenstates and the constant an is called an

Eigenvalue.
Example 4
(a) Show that the operator J^z when it acts on j Zi it won’t change the state
j Zi : It just simply add a constant. That means
J^z j Zi = C j Zi (3.41)
and the value of this constant is C = ~=2.
(b) For J^z j Zi = ~

2 j Zi show that
^ ('^
R z ) j+Xi = Constant j+Y i
for ' = =2
(c) Show that for J^y j Y i = ~2 j Y i and a rotation of the state j+Zi about
the y axis in a counterclockwise direction by ' = =2
^
R j j+Zi = j+Xi : (3.42)
2
Solution:
(a) First let’s show that the e¤ect of J^z on j Zi is to add a multiplying factor to
the state j Zi without changing the state. Consider the rotation operator
R^ ('k)
2
^ ('k) = 1 i'Jz + 1 i'Jz
R + ::: (3.43)
~ 2! ~
When this operator acts on j Zi ; we have
!
2
^ ('k) j Zi = i'Jz 1 i'Jz
R 1 + + ::: j Zi
~ 2! ~
2
^ ('k) j Zi = 1 j Zi i' ^ 1 i'
R Jz j Zi + J^z2 j Zi + ::: (3.44)
~ 2! ~
Physically we know that for spin- 21 particle with spin along the positive z
axis if we apply a magnetic …eld along the z-direction it would not change
the state (Virtual Experiment 1). Therefore, we must expect that
^ ('k) j Zi = constant j Zi :
R (3.45)
But just to convince ourselves this is actually true, let’s say that J^z changes
the state j Zi to a di¤erent state, for example, j Xi, which we may
express as
J^z j Zi = ~ j Xi : (3.46)
Then the action of the rotation operator on j Zi would result in
^ ('k) j Zi = 1 j Zi 1 2
R ( i') j Xi + ( i') j Xi + :: (3.47)
2!
But physically since we expect
^ ('k) j Zi = constant j Zi :
R (3.48)
which suggests, we must have

1 2
( i') j Xi + ( i') j Xi + ::: = 0 (3.49)
2!
and
^ ('^
R z ) j Zi = j Zi
that makes R^ ('^
z ) be an identity operator which is not true. Thus J^z
would not change the state j Zi into a di¤erent state. It must then add
some complex factor like an eigenvalue equations
J^z j Zi = C j Zi ; J^z2 j Zi = C 2 j Zi ; ::: (3.50)
This leads to
2
^ ('k) j Zi = 1 j Zi i'C j Zi + 1 i'C
R j Zi + :::
~ 2! ~
" #
2
^ i'C 1 i'C
R ('k) j Zi = 1 + + ::: j Zi
~ 2! ~
= Constant j Zi : (3.51)
(b) In SG experiment we saw that

~ ~
J^z j Zi = j Zi ) C = (3.52)
2 2
Physically if we rotate the state j+Xi about the z axis with ' = =2; we
expect j+Y i : Which means
^ ('k) j+Xi = Constant j+Y i :
R (3.53)
If we can show that R ^ ('k) j Xi =Constantj+Y i is true for J^z j Zi =

~ ~
2 j Zi then it means we have shown that C = 2 : Consider the state
1 1
j+Xi = p j+Zi + p j Zi (3.54)
2 2
then
R^ ('k) j+Xi = p1 R ^ ('k) j+Zi + p1 R ^ ('k) j Zi

2 2
0 !2 1
1 @ i'J^z 1 i'J^z
=p 1 + + :::A j+Zi
2 ~ 2! ~
0 !2 1
1 @ i'J^z 1 i'J^z
+p 1 + + :::A j Zi
2 ~ 2! ~
0 !2 1
1 @ i'J^z 1 i'J^z
=p 1 j+Zi j+Zi + j+Zi + :::A
2 ~ 2! ~
0 !2 1
1 @ i'J^z 1 i'J^z
+p 1 j Zi j Zi + j Zi + :::A
2 ~ 2! ~
!
2
1 i' 1 i'
=p 1 j+Zi j+Zi + j+Zi + :::
2 2 2! 2
!
2
1 i' 1 i'
+p 1 j Zi + j Zi + j Zi + ::: (3.55)
2 2 2! 2
!
2
) ^ ('k) j+Xi = p1
R 1
i'
+
1 i'
+ ::: j+Zi
2 2 2! 2
!
2
1 i' 1 i'
+p 1+ + + ::: j Zi
2 2 2! 2
) ^ ('k) j+Xi = p1 e
R i'=2 1
j+Zi + p ei'=2 j Zi (3.56)
2 2
^ ('k) j+Xi = e i'=2 1 1

)R p j+Zi + p ei' j Zi (3.57)
2 2
For a rotation ' 6= 0, we see that the state is clearly a di¤erent state. For
' = =2; we …nd
^ i =4 1 1
R k j+Xi = e p j+Zi + p ei =2 j Zi
2 2 2
i =4 1 i
= e p j+Zi + p j Zi (3.58)
2 2
Referring to chapter two we know that
1 i
j+Y i = p j+Zi + p j Zi (3.59)
2 2
Therefore
^
R k j+Xi = e i =4
j+Y i (3.60)
2
and this shows that indeed the eigenvalues of J^z are ~=2
~
J^z j Zi = j Zi : (3.61)
2
by applying the identity operator. again physically this must lead to the
state j+Xi :
(c) Since the rotation operator about the y axis is
!2
^ ('j) = 1 i'J^y 1 i'J^y
R + + :::
~ 2! ~
and
~
J^y j Y i = j Y i: (3.62)
2
we should express the state j+Zi in terms of the basis vectors j Y i :Recalling
that
1 1
j+Y i = p (j+Zi + i j Zi) ; j Y i = p (j+Zi i j Zi) (3.63)
2 2
we have
1 i
j+Zi = p (j+Y i + j Y i) ; j Zi = p (j+Y i j Y i) (3.64)
2 2
then
R^ ('j) j+Zi = p1 R ^ ('j) j+Y i + p1 R ^ ('j) j Y i

2 2
0 !2 1
1 i'Jy^ 1 i'Jy ^
= p @1 + + :::A j+Y i
2 ~ 2! ~
0 !2 1
1 i'Jy^ 1 i'Jy ^
+ p @1 + + :::A j Y i
2 ~ 2! ~
0 !2 1
1 i'Jy^ 1 i'Jy ^
= p @1 j+Y i j+Y i + j+Y i + :::A
2 ~ 2! ~
0 !2 1
1 i'Jy^ 1 i'Jy ^
+ p @1 j Y i j Yi+ j Y i + :::A
2 ~ 2! ~
!
2
1 i' 1 i'
=p 1 j+Y i j+Y i + j+Y i + :::
2 2 2! 2
!
2
1 i' 1 i'
+p 1j Y i + j Yi+ j Y i + ::: (3.65)
2 2 2! 2
!
2
^ ('j) j+Zi = p1
) R 1
i'
+
1 i'
+ ::: j+Y i
2 2 2! 2
!
2
1 i' 1 i'
+p 1+ + + ::: j Y i
2 2 2! 2
^ ('^ 1 i'=2 1
) R z ) j+Zi = p e j+Y i + p ei'=2 j Y i (3.66)
2 2
For ' = =2, we …nd
^ 1 h
R j j+Zi = p cos i cos j+Y i
2 2 4 4
i
+ cos + i cos j Yi
4 4
1 1 i
= p p (j+Y i + j Y i) + p (j+Y i j Y i)(3.67)
:
2 2 2
Recalling that
1 i
j+Zi = p (j+Y i + j Y i) ; j Zi = p (j+Y i j Y i) (3.68)
2 2
one …nds
^ 1
R j j+Zi = p (j+Zi + j Zi) = j+Xi : (3.69)
2 2
3.3 The identity and projection operators

The identity operator (often referred as the completeness relation): an operator
that acts on the ket vector and does nothing. In our discussion of completeness
of orthonormal basis we have seen that any state j i can be expressed as a linear
superposition of the orthonormal basis vectors ja1 i ; ja2 i ; ja3 i :::. For example
in the case of spin- 21 particles we have seen that the state j i in the Sz basis
can be expressed as
j i = c+ j+Zi + c j Zi (3.70)
or using
c+ = h+Z j i ; c = h Z j i (3.71)
j i = h+Z j i j+Zi + h Z j i j Zi = j+Zi h+Z j i + j Zi h Z j i

) j i = (j+Zi h+Zj + j Zi h Zj) j i = I^ j i = j i (3.72)
where
I^ = j+Zi h+Zj + j Zi h Zj (3.73)
is the identity operator which does nothing to the state j i : A nice physical
mechanism for inserting such an identity operator without changing the state of
a spin- 21 system is the Faynman’s modi…ed SG apparatus for spin-1/2 particles..
The projection operator : the identity operator may be viewed as composed
of two projection operators
P^+ = j+Zi h+Zj ; P^ = j Zi h Zj ) I^ = P^+ + P^ (3.74)
since each of these operators take a state j i and projects it along the directions
j+Zi and j Zi ; respectively
P^+ j i = j+Zi h+Zj i = c+ j+Zi ; P^ j i = j Zi h Zj i = c j Zi (3.75)
Suppose the state of the spin- 12 particle is j i = j+Zi, then the e¤ect of the
projection operators will be
P^+ j+Zi = j+Zi h+Zj +Zi = 1 j+Zi ; P^+ j Zi = j+Zi h+Zj Zi = 0 j Zi

(3.76)
Therefore j+Zi and j Zi are the eigenstates of P^+ with the corresponding
eigenvalues 1 and 0; respectively: Similarly if its state is j i = j Zi ; we …nd
P^ j+Zi = j Zi h Zj +Zi = 0 j+Zi ; P^ j Zi = j Zi h Zj Zi = 1 j Zi ;

(3.77)
which shows that j+Zi and j Zi are the eigenstates of P^ with eigenvalues 0
and 1, respectively:
Each of spin- 21 particles that traversed one of the projection devices is cer-
tainly pass through a second device of same kind but can not pass through a
3.3. THE IDENTITY AND PROJECTION OPERATORS 63
second device of opposite kind. This can be shown using the two projection
operators, P^+ and P^ ;
P^+2 = (j+Zi h+Zj) (j+Zi h+Zj) = j+Zi h+Zj +Zi h+Zj = j+Zi h+Zj
) P^+2 = P^+ ; (Passing through same device)
P^ 2 = (j Zi h Zj) (j Zi h Zj) = j Zi h Zj Zi h Zj = j Zi h Zj
) P^ 2 = P^ ; (Passing through same device) (3.78)
P^+ P^ = (j+Zi h+Zj) (j Zi h Zj) = j+Zi h+Zj Zi h Zj

) P^+ P^ = 0; (Passing through di¤erent device)
P^ P^+ = (j Zi h Zj) (j+Zi h+Zj) = j Zi h Zj +Zi h+Zj
) P^ P^+ = 0; (Passing through di¤erent device) (3.79)
More identity operators: What we have seen so far is the identity operator
in the Sz basis
j+Zi h+Zj + j Zi h Zj = 1: (3.80)
But we can also write the identity operator in the Sx basis,
j+Xi h+Xj + j Xi h Xj = 1: (3.81)
or in the Sy basis
j+Y i h+Y j + j Y i h Y j = 1: (3.82)
Example 5 Determine j+Y i and j Y i using the states j+Xi and j Xi as

basis vectors.
Solution: We recall that j+Y i and j Y i in j+Zi and j Zi basis vectors are
given by
1 1
j+Y i = p (j+Zi + i j Zi) ; j Y i = p (j+Zi i j Zi) (3.83)
2 2
Using the identity operator for the Sx basis,
j+Xi h+Xj + j Xi h Xj = 1: (3.84)
one can write

1 1
j+Y i = p (j+Xi h+Xj + j Xi h Xj) (j+Zi + i j Zi) = p [j+Xi h+Xj +Zi
2 2
(3.85)
= + j Xi h Xj +Zi + i j+Xi h+Xj Zi + i j Xi h Xj Zi] ; (3.86)
Using
1 1
j+Xi = p (j+Zi + j Zi) ; j Xi = p (j+Zi j Zi)
2 2
we have
1 1
h+Xj +Zi = p (h+Zj +Zi + h Zj +Zi) = p
2 2
1 1
h Xj +Zi = p (h+Zj +Zi h Zj +Zi) = p
2 2
1 1
h+Xj Zi = p (h+Zj Zi + h Zj Zi) = p
2 2
1 1
h Xj Zi = p (h+Zj Zi h Zj Zi) = p
2 2
so that
1
j+Y i = (j+Xi + j Xi + i j+Xi i j Xi) (3.87)
2
1
= [(1 + i) j+Xi + (1 i) j Xi] ; (3.88)
2
You can follow a similar procedure to express j Y i in j+Xi and j Xi
basis vectors.
Example 6 Applying the identity operator in the Sz basis and J^y j Y i =

~
2 j Yi
(a) show that

h i
^ ('j) j+Zi = p1 e
R
i'
2 j+Y i + e
i'
2 j Yi
2
(b) For ' = =2, show that

^ ('j) j+Zi = j+Xi
R
(c) Homework : Following a similar procedure show that
^
R j j Zi = j Xi
2
Solution:
(a) For a rotation about the y axis

!2
^ ('j) = 1 i'J^y 1 i'J^y
R + + :::
~ 2! ~
we have
!2
^ ('j) j+Zi = 1 j+Zi i'J^y 1 i'J^y
R j+Zi + j+Zi + :::
~ 2! ~
3.3. THE IDENTITY AND PROJECTION OPERATORS 65
so that using the identity operator in the Sy basis, we may write
R^ ('j) j+Zi = 1 (j+Y i h+Y j + j Y i h Y j) j+Zi

!2
i'J^y 1 i'J^y
(j+Y i h+Y j + j Y i h Y j) j+Zi + (j+Y i h+Y j + j Y i h Y j) j+Zi + :::
~ 2! ~
(3.89)
^ ('j) j+Zi = h+Y j +Zi j+Y i + h Y j +Zi j Y i

R
i'J^y
(h+Y j +Zi j+Y i + h Y j +Zi j Y i)
~
!2
1 i'J^y
+ (h+Y j +Zi j+Y i + h Y j +Zi j Y i)(3.90)
+ :::
2! ~
^ ('j) j+Zi = h+Y j +Zi j+Y i i'

R h+Y j +Zi J^y j+Y i
~
2
1 i'
+ h+Y j +Zi J^y2 j+Y i
2! ~
2
i' 1 i'
+ h Y j +Zi j Y i h Y j +Zi J^y j Y i + h Y j +Zi J^y2 j Y i + :::
~ 2! ~
(3.91)
Noting that
~
J^y j Y i = j Y i; (3.92)
2
one …nds
" #
2
^ i' 1 i'
R ('j) j+Zi = h+Y j +Zi j+Y i j+Y i + j+Y i + :::
2 2! 2
" #
2
i' 1 i'
+ h Y j +Zi j Y i + j Yi+ j Y i + ::: (3.93)
2 2! 2
" #
2
^ i' 1 i'
R j j+Zi = h+Y j +Zi 1 + + ::: j+Y i
2 2 2! 2
" #
2
i' 1 i'
+ h Y j +Zi 1 + + + ::: j Y i
2 2! 2
i' i'
^ ('j) j+Zi = h+Y j +Zi e
)R 2 j+Y i + h Y j +Zi e 2 j Yi (3.94)
and using
1 1
h+Y j +Zi = p ; h Y j +Zi = p (3.95)
2 2
we …nd h i
^ ('j) j+Zi = p1 e
R
i'
2 j+Y i + e
i'
2 j Yi (3.96)
2
(b) Using the identity operator in Sx basis,
j+Xi h+Xj + j Xi h Xj = I: (3.97)
we may write
^ 1 n i
R j j+Zi = p e [j+Xi h+Xj +Y i + j Xi h Xj +Y i]
4
2 2
i
o
+e 4 [j+Xi h+Xj Y i + j Xi h Xj Y i] (3.98)
so that using
1 1 1
h+Xj +Y i = p (h+Zj + h Zj) p (j+Zi + i j Zi) = (1 + i)
2 2 2
1 i
) h+Xj +Y i = p e 4 = h Xj Y i
2
1 1 1
h Xj +Y i = p (h+Zj h Zj) p (j+Zi + i j Zi) = (1 i)
2 2 2
1 i4
) h Xj +Y i = p e = h+Xj Y i (3.99)
2
we …nd
^ 1 i 1 1
R j j+Zi = p e 4 p ei 4 j+Xi + p e i 4 j Xi
2 2 2 2
i 1 1
+e 4 p e i 4 j+Xi + p ei 4 j Xi (3.100)
2 2
^ 1 1 1
R j j+Zi = p p j+Xi + p e i 2 j Xi
2 2 2 2
1 1 i
+ p j+Xi + p e 2 j Xi = j+Xi(3.101)
2 2
3.4 Matrix Representation of Operators

We have seen that the ket vectors can be represented by a column matrix and
the bra vector by a row matrix. For example the state vector j i in the Sz basis
vectors j+Zi and j Zi, using the identity operator, can be expressed as
h+Zj i
j i = j+Zi h+Zj i + j Zi h Zj i = (3.102)
h Zj i
3.4. MATRIX REPRESENTATION OF OPERATORS 67
and the corresponding bra vector row matrix, which is the transpose and con-
jugate of the ket vector column matrix, is
h j = h j +Zi h+Zj + h j Zi h Zj = h j +Zi h j Zi (3.103)
For the sake of simplicity suppose we represent j+Zi and j Zi by ja1 i and ja2 i,
respectively, one may write the identity operators for the Sz basis vectors as
2
X
jai i hai j = 1 (3.104)
i=1
so that
2
X 2
X ha1 j i c1
j i = jai i hai j i = ci jai i = = (3.105)
ha2 j i c2
i=1 i=1
2
X 2
X
h j = h j aj i haj j = cj haj j = h j a1 i h j a2 i = c1 (3.106)
c2
j=1 j=1
The operator A: Operators can also be represented by matrices using di¤er-

ent basis. Consider an operator A:^ In general, the e¤ect of an operator when it
acts on a ket vector j i is to change the vector into a di¤erent ket j'i,
A^ j i = j'i : (3.107)
Using the identity operator in the Sz basis we can also write

2
X 2
X ha1 j 'i b1
j'i = jai i hai j 'i = bi jai i = = (3.108)
ha2 j 'i b2
i=1 i=1
2
X
h'j = h'j aj i haj j = h'j a1 i h'j a2 i = b1 b2 (3.109)
j=1
and
2
X 2
X ha1 j 'i b1
A^ j i = A^ jai i hai j i = ci A^ jai i = = : (3.110)
ha2 j 'i b2
i=1 i=1
Then using h j, one can write
2 X
X 2 2 X
X 2 2
X
h j 'i = cj bi haj j ai i = cj bi ij = ci bi
i=1 j=1 i=1 j=1 i=1
b1 ha1 j 'i
) h j 'i = c1 c2 = h j a1 i h j a2 i (3.111)
b2 ha2 j 'i
and
2
X 2
X 2 X
X 2
h j A^ j i = cj haj j ci A^ jai i = cj haj j A^ jai i ci
j=1 i=1 i=1 j=1
ha1 j A^ ja1 i ha1 j A^ ja2 i c1

) h j A^ j i = c1 c2 (3.112)
ha2 j A^ ja1 i ha2 j A^ ja2 i c2
ha1 j A^ ja1 i ha1 j A^ ja2 i ha1 j i
) h j A^ j i = h j a1 i h j a2 i
(3.113)
so that from
A^ j i = j'i ) h j A^ j i = h j 'i : (3.114)
one …nds

h j a1 i h j a2 i
ha1 j 'i
= h j a1 i h j a2 i (3.115)
ha2 j 'i
There follows that
ha1 j A^ ja1 i ha1 j A^ ja2 i ha1 j i ha1 j 'i

= ; (3.116)
ha2 j A^ ja1 i ha2 j A^ ja2 i ha2 j i ha2 j 'i
which is the matrix form of the equation
A^ j i = j'i :
and the matrix
A11 A12 ha1 j A^ ja1 i ha1 j A^ ja2 i

A= = (3.117)
is the matrix representation of the operator Â using the basis vectors ja1 i
(j+Zi)and ja2 i (j Zi) which form a complete set.
One can also show this without using the summation notation in the follow-
ing way.
h j A^ j i = (h j +Zi h+Zj + h j Zi h Zj) A^ (j+Zi h+Zj i + j Zi h Zj i)

= (h j +Zi h+Zj + h j Zi h Zj) (j+Zi h+Zj 'i + j Zi h Zj 'i) : (3.118)
so that upon expanding we …nd
h j A^ j i = h j +Zi h+Zj A^ j+Zi h+Zj i + h j Zi h Zj A^ j+Zi h+Zj i

+ h j +Zi h+Zj A^ j Zi h Zj i + h j Zi h Zj A^ j Zi h Zj i : (3.119)
We can also write
h j A^ j i = h j 'i
= h j +Zi h+Zj +Zi h+Zj 'i + h j Zi h Zj +Zi h+Zj 'i
+ h j +Zi h+Zj Zi h Zj 'i + h j Zi h Zj Zi h Zj 'i : (3.120)
which leads to
h j +Zi h+Zj A^ j+Zi h+Zj i + h j Zi h Zj A^ j+Zi h+Zj i

+ h j +Zi h+Zj A^ j Zi h Zj i + h j Zi h Zj A^ j Zi h Zj i
+ h j +Zi h+Zj Zi h Zj 'i + h j Zi h Zj Zi h Zj 'i : (3.121)
) h j +Zi h+Zj A^ j+Zi h+Zj i + h j Zi h Zj A^ j+Zi h+Zj i

+ h j +Zi h+Zj A^ j Zi h Zj i + h j Zi h Zj A^ j Zi h Zj i
+ h j +Zi h+Zj Zi h Zj 'i + h j Zi h Zj Zi h Zj 'i (3.122)
h i
) h j +Zi h+Zj A^ j+Zi + h j Zi h Zj A^ j+Zi h+Zj i
h i
+ h j +Zi h+Zj A^ j Zi + h j Zi h Zj A^ j Zi h Zj i
= [h j +Zi h+Zj +Zi + h j Zi h Zj +Zi] h+Zj 'i
+ [h j +Zi h+Zj Zi + h j Zi h Zj Zi] h Zj 'i (3.123)
Using the matrix representation for the ket vector j i
h+Zj i
j i= (3.124)
h Zj i
and the bra vector h j
h j= h j +Zi h j Zi (3.125)
the above expression in matrix for can be written as
h+Zj A^ j+Zi h+Zj A^ j Zi

h j +Zi h j Zi
h Zj A^ j+Zi h Zj A^ j Zi
h+Zj i
h Zj i
h+Zj +Zi h+Zj Zi
= h j +Zi h j Zi
h Zj +Zi h Zj Zi
h+Zj 'i
(3.126)
h Zj 'i
h+Zj A^ j+Zi h+Zj A^ j Zi h+Zj i

)
h Zj A^ j+Zi h Zj A^ j Zi h Zj i
h+Zj +Zi h+Zj Zi h+Zj 'i
= (3.127)
h Zj +Zi h Zj Zi h Zj 'i
Noting that h+Zj +Zi = h Zj Zi = 1 and h+Zj Zi = h Zj +Zi = 0; we

…nd the matrix form of the identity operator in the Sz basis
1 0
=1 (3.128)
0 1
so that
h+Zj A^ j+Zi h+Zj A^ j Zi h+Zj i h+Zj 'i

=1
h Zj A^ j+Zi h Zj A^ j Zi h Zj i h Zj 'i
h+Zj A^ j+Zi h+Zj A^ j Zi h+Zj i h+Zj 'i
) = (3.129)
h Zj A^ j+Zi h Zj A^ j Zi h Zj i h Zj 'i
Which is the matrix form of the equation
A^ j i = j'i : (3.130)
The matrix representation for the adjoint operator A^y : For an operator A^
the matrix representation of its adjoint operator A^y is the transpose conjugate
^ If the matrix elements for a operator A^ in basis
of the matrix representing A:
jji are
Aij = hij A^ jji (3.131)
then the matrix element for the adjoint operator A^y are given by
Ayij = hij A^y jji = hjj A^ jii : (3.132)
Proof: If an operator A^ satis…es
A^ jii = jki (3.133)
then by de…nition the adjoint operator
hij A^y = hkj : (3.134)
Then multiplying the above two equations by hjj and jji, respectively we …nd
hjj A^ jii = hjj ki ; hij A^y jji = hkj ji : (3.135)
We recall
hkj ji = hjj ki (3.136)
so that
hij A^y jji = hkj ji = hjj ki = hjj A^ jii (3.137)
Hermitian operators ( A^y = A):

^ For any Hermitian operator, A^y = A^
hij A^y jji = hjj A^ jii ) hij A^ jji = hjj A^ jii : (3.138)
This means for any Hermitian operators the matrix representation is equals to
its transpose conjugate.
Multi operators product (ÂB̂): if we know the matrix representations for each
of the matrices A^ and B,
^ then the matrix representation of an operator C^ = A^B^
is just the product of the matrices of the two operators in the given order. This
is shown below:
hij C^ jji = hij A^B
^ jji (3.139)
Using the identity operator for the basis used to represent the matrices
X
jki hkj = 1 (3.140)
k
we can write
X X
hij C^ jji = hij A^ ^ jji =
jki hkj B hij A^ jki hkj B
^ jji
k k
X
) hij C^ jji = Aik Bkj (3.141)
k
The adjoint of Multi operators product (ÂB̂): The adjoint of the product of
two operators: the adjoint of the operator C^ = A^B
^ is given by
y
C^ y = A^B
^ ^ y A^y :
=B (3.142)
This can be shown as follows: Recalling that
hjj A^y jii = hij A^ jji (3.143)
we may write
hjj C^ y jii = hij C^ jji (3.144)
and applying
X X
hij C^ jji = hij A^ jki hkj B
^ jji = Aik Bkj
k k
we can write
" #
X X
hjj C^ y jii = hij A^ jki hkj B
^ jji = hij A^ jki hkj B
^ jji (3.145)
k k
But we know
hij A^ jki = hkj A^y jii ; hkj B
^ jji = hjj B
^ y jki (3.146)
which leads to
X X
hjj C^ y jii = hkj A^y jii hjj B
^ y jki ) hjj C^ y jii = ^ y jki hkj A^y jii
hjj B
k k
!
X
) hjj C^ y jii = hjj B
^y jki hkj A^y jii
k
Noting that X
jki hkj = 1
k
we …nd
y
hjj C^ y jii = hjj B
^ y A^y jii ) C^ y = B
^ y A^y ) A^B
^ ^ y A^y
=B (3.147)
Example 7 Find the matrix representation of the operators P^+ and J^z
(a) In the Sx basis
(b) In the Sy basis
Solution:
(a) In the Sx basis we have j1i = j+Xi and j2i = j Xi given by

1 1 1 1
j+Xi = p j+Zi + p j Zi ; j Xi = p j+Zi p j Zi : (3.148)
2 2 2 2
For the projection operator
P^+ = j+Zi h+Zj ; (3.149)
the matrix elements
hij P^+ jji = hi j+Zi h+Zj jji ; (3.150)
can easily be determined as follows
1 1
h1j +Zi h+Z j1i = p h+Zj + p h Zj j+Zi h+Zj
2 2
1 1 1
p j+Zi + p j Zi = (3.151)
2 2 2
1 1
2 2
1 1 1
p j+Zi p j Zi = (3.152)
2 2 2
1 1
h2j +Zi h+Z j1i = p h+Zj p h Zj j+Zi h+Zj
2 2
1 1 1
p j+Zi + p j Zi = (3.153)
2 2 2
1 1
2 2
1 1 1
p j+Zi p j Zi = (3.154)
2 2 2
where we used the relations
hij ji = ij
for the Sz basis vectors. The matrix representation of the projection op-
erator P^+ will then be
1 1 1
2 2 1 1
P+ = 1 1 = :
2 2 2 1 1
For the operator J^z ; using the relations

~
J^z j Zi = j Zi (3.155)
2
one can also show that
1 1 1 1
h1j J^z j1i = p h+Zj + p h Zj J^z p j+Zi + p j Zi = 0;
2 2 2 2
1 1 1 1 ~
h1j J^z j2i = p h+Zj + p h Zj J^z p j+Zi p j Zi = ;
2 2 2 2 2
1 1 1 1 ~
h2j J^z j1i = p h+Zj p h Zj J^z p j+Zi + p j Zi = ;
2 2 2 2 2
1 1 1 1
h2j J^z j2i = p h+Zj p h Zj J^z p j+Zi p j Zi = 0:
2 2 2 2
(3.156)
For the operator J^z which is a Hermitian operator, to …nd the none di-
agonal elements of the matrix, we can use the properties of Hermitian
operators
hij A^y jji = hjj A^ jii ) hij A^ jji = hjj A^ jii (3.157)
which shows
~
h2j J^z j1i = h1j J^z j2i = :
2
The matrix representation for the operator Jz is^
~ ~
0 0 1
J^z = ~
2 =
2 0 2 1 0
1 i 1 i
j+Y i = p j+Zi + p j Zi ; j Y i = p j+Zi p j Zi
2 2 2 2
(b) Using the Sy basis
1 i
j+Y i = p j+Zi + p j Zi = j1i ;
2 2
1 i
j Yi = p j+Zi p j Zi = j2i ;
2 2
one can show, following a similar procedure,
1 i
2 2
1 i 1
p j+Zi + p j Zi = (3.158)
2 2 2
1 i
2 2
1 i 1
p j+Zi p j Zi = = h2j +Zi h+Z j1i (3.159)
2 2 2
1 i
2 2
1 i 1
p j+Zi p j Zi = (3.160)
2 2 2
and the matrix representation is found to be the same
1 1 1
2 2 1 1
P+ = 1 1 = : (3.161)
2 2 2 1 1
On the other hand for the operator J^z , we have

1 i 1 i
h1j J^z j1i = p h+Zj p h Zj J^z p j+Zi + p j Zi = 0;
2 2 2 2
1 i 1 i
h1j J^z j2i = p h+Zj p h Zj J^z p j+Zi p j Zi
2 2 2 2
~
= = h2j J^z j1i ;
2
1 i 1 i
h2j J^z j2i = p h+Zj + p h Zj J^z p j+Zi p j Zi = 0:
2 2 2 2
(3.162)
which also gives same matrix
~ ~
0 0 1
J^z = ~
2 = :
2 0 2 1 0
3.5. CHANGING REPRESENTATIONS 75
3.5 Changing representations

...it is all about the completeness relation....
State vectors: Consider one set of basis vectors fja1 i ; ja2 i ; ::: jaN ig and
second di¤erent set of vectors fjb1 i ; jb2 i ; ::: jbN ig : Each of these set of vectors
form a complete set in its own Hilbert space. That means
N
X N
X
jan i han j = 1 and jbn i hbn j = 1: (3.163)
n=1 n=1
We have already seen that if we have a vector j i describing the state of a given
system, like the spin-half particle, this state can be expressed using any of these
two di¤erent set of basis vectors. All we need to do is to apply the completeness
relation for these basis vectors
N
X N
X N
X
j i= jan i han j i = han j i jan i = cn jan i ; (3.164)
n=1 n=1 n=1
or
N
X N
X N
X
j i= jbn i hbn j i = hbn j i jbn i = dn jan i ; (3.165)
n=1 n=1 n=1
where
cn = han j i ; dn = hbn j i :
This state ket vector using matrix representation can also be expressed as
0 1
ha1 j i
B ha2 j i C
B C
B ha3 j i C
B C
j i=B B : C
C (3.166)
B : C
B C
@ : A
haN j i
in the jan i basis or 0 1

hb1 j i
B hb2 j i C
B C
B hb3 j i C
B C
j i=B
B : C
C (3.167)
B : C
B C
@ : A
hbN j i
in the jbn i basis with the corresponding state bra vectors
h j= h j a1 i h j a2 i h j a3 i ::: h j aN i (3.168)
and
h j= h j b1 i h j b2 i h j b3 i ::: h j bN i ; (3.169)
respectively. If we want to go from one basis to another, all we have to do is
to insert the appropriate completeness relation at the appropriate place. For
example if we want to go from jan i basis where
N
X
j i= cn jan i (3.170)
n=1
to jbn i basis, we insert the completeness relation for these basis

N
X
jbm i hbm j = 1 (3.171)
m=1
so that
N N N
"N #
X X X X
j i = han j i jbm i hbm j an i = hbm j an i han j i jbm i
n=1 m=1 m=1 n=1
N
X
) j i= cm jbm i : (3.172)
m=1
In matrix representation we may write this as

0 1
c1
B c2 C
B C
B c3 C
B C
j i=B B : C;
C (3.173)
B : C
B C
@ : A
cN
where
1 0
ha1 j i
B ha2 j i C
N B C
X B ha3 j i C
cm = B
hbm j an i han j i = hbm j a1 i hbm j a2 i hbm j a3 i ::: B C:
: C
n=1 B C
@ : A
:
(3.174)
Operators: From our discussion of matrix representation we recall that for
an operator A;^ the matrix representation in the basis, for example fja1 i ; ja2 ig
(like the Sz basis for spin-half particles), is given by
fja1 i;ja2 ig A11 A12 ha1 j A^ ja1 i ha1 j A^ ja2 i

A^ ! A= = ; (3.175)
where the state vector is expressed in terms of these basis vectors

2
X
j i= cn jan i . (3.176)
n=1
But somebody else has the state vector is expressed in terms of a di¤erent basis
vectors fjb1 i ; jb2 ig (like the SX basis for spin-half particles)
2
X
j i= dn jbn i . (3.177)
n=1
And obviously he/she wants to express the same operator in the basis fjb1 i ; jb2 ig :
Now the question is is there any relationship between these two di¤erent matrix
representation for the same operators? The answer must be yes because this
operator represent a measurable physical quantity in quantum mechanics and
the outcome of the measurement for this physical quantity must be the same
under same physical conditions. Di¤erent representation of the same state of a
system may require di¤erent mechanisms or instrument but whatever is mea-
sured must not change. So let’s seek for the mathematical equation in a matrix
form that describes the relationship between these two representation. As I said
at the beginning, it is all depend on the completeness of the basis vectors.
Suppose in the basis fjb1 i ; jb2 i ; ::: jbN ig ; for the matrix representation of
^ one determined the elements of the matrix to be
the operator A;
A0 = hbi j A^ jbj i :
ij (3.178)
Using the completeness relation for the basis fja1 i ; ja2 i ; ::: jaN ig, twice
N
X N
X
jam i ham j = 1; jam i ham j = 1 (3.179)
m=1 m=1
where I considered N basis states instead of two, for the sake of generalization,
one can write
N
X N
X N X
X N
A0ij = hbi j jam i ham j A^ jam i ham j bj i = hbi j am i ham j A^ jam i ham j bj i :
m=1 m=1 m=1 m=1
(3.180)
Let’s limit our basis vectors to the spin-half particles so that one can write
2 X
X 2
A011 = hb1 j am i ham j A^ jam i ham j b1 i
m=1 m=1
ha1 j A^ ja1 i ha1 j A^ ja2 i ha1 j b1 i

= hb1 j a1 i hb1 j a2 i (3.181)
:
2 X
X 2
m=1 m=1

= hb1 j a1 i hb1 j a2 i (3.182)
:
2 X
X 2
m=1 m=1

= hb2 j a1 i hb2 j a2 i (3.183)
:
2 X
X 2
m=1 m=1

= hb2 j a1 i hb2 j a2 i (3.184)
:
These four equation can be easily combined to give the following matrix equation
A011 A012 hb1 j A^ jb1 i hb1 j A^ jb2 i

=
A021 A022 hb2 j A^ jb1 i hb2 j A^ jb2 i
hb1 j a1 i hb1 j a2 i ha1 j A^ ja1 i ha1 j A^ ja2 i ha1 j b1 i ha1 j b2 i
=
hb2 j a1 i hb2 j a2 i ha2 j A^ ja1 i ha2 j A^ ja2 i ha2 j b1 i ha2 j b2 i
(3.185)
Suppose we represent the third matrix in the above expression by T ,
ha1 j b1 i ha1 j b2 i
T = (3.186)
then for T y , which is the transpose conjugate matrix of T, we …nd

y
ha1 j b1 i ha1 j b2 i ha1 j b1 i ha2 j b1 i
Ty = =
ha2 j b1 i ha2 j b2 i ha1 j b2 i ha2 j b2 i
hb1 j a1 i hb1 j a2 i
) Ty = (3.187)
hb2 j a1 i hb2 j a2 i
Therefore the transformation equation from the basis fja1 i ; ja2 i ; ::: jaN ig rep-
resentation of the operator A^ to the basis fjb1 i ; jb2 i ; ::: jbN ig representation can
be expressed
A0 = T y AT
where
hb1 j A^ jb1 i hb1 j A^ jb2 i ha1 j A^ ja1 i ha1 j A^ ja2 i
A0 = ;A = ;
hb2 j A^ jb1 i hb2 j A^ jb2 i ha2 j A^ ja1 i ha2 j A^ ja2 i
T = :
Noting that each basis set of vectors are orthonormal set
hbi j bj i = ij
upon using the completeness relation for the basis fja1 i ; ja2 i ; ::: jaN ig
N
X
jam i ham j = 1; (3.188)
m=1
one can write

N
X N
X
hbi j jam i ham j bj i = hbi j am i ham j bj i = ij
m=1 m=1
Once again if we limit to a set of two basis vectors, we have

N
X ha1 j b1 i
hb1 j am i ham j b1 i = hb1 j a1 i hb1 j a2 i = 11 =1
ha2 j b1 i
m=1
N
X ha1 j b2 i
ha2 j b2 i
m=1
N
X ha1 j b1 i
ha2 j b1 i
m=1
N
X ha1 j b2 i
hb2 j am i ham j b2 i = hb2 j a1 i hb2 j a2 i = 22 =
(3.189)
1
ha2 j b2 i
m=1
so that in matrix form one can write

hb1 j a1 i hb1 j a2 i ha1 j b1 i ha1 j b2 i 1 0
=
hb2 j a1 i hb2 j a2 i ha2 j b1 i ha2 j b2 i 0 1
T yT = T T y = I (3.190)
1
We recall from Theoretical physics I, the inverse matrix T ;
1 1
T T = TT = I: (3.191)
This shows that for the transformation matrix T , we …nd

1
T = T y:
which tells us the transformation matrix from one basis to another must be
an orthogonal matrix like the rotation matrix we saw in Chapter I and also in
Theoretical physics I. So basically what one can conclude from representation
of state vector or an operator on one basis or another is basically represent the
same vector described in one coordinate system or another obtained coordinates
system in Hilbert space obtained by simple rotation about some axis.
Example 8 Determine the matrix representation of the operator J^x in the

basis (i.e fjb1 i ; jb2 ig = fj+Zi ; j Zig) from the matrix representation of
J^x basis (i.e fja1 i ; ja2 ig = fj+Xi ; j Xig).
Solution: we recall that Noting that

1 1 1 1
ja1 i = j+Xi = p j+Zi + p j Zi ) ha1 j = p h+Zj + p h(3.192)
Zj ;
2 2 2 2
1 1 1 1
ja2 i = j Xi = p j+Zi p j Zi ) ha2 j = p h+Zj p h(3.193)
Zj ; :
2 2 2 2
so that using
jb1 i = j+Zi ; jb2 i = j Zi (3.194)
one can write the matrix representation for J^x in the basis (i.e fja1 i ; ja2 ig =
fj+Xi ; j Xig) as
ha1 j J^x ja1 i ha1 j J^x ja2 i ~ 1 0

Jx = = (3.195)
ha2 j J^x ja1 i ha2 j J^x ja2 i 2 0 1
and the transformation matrix

ha1 j b1 i ha1 j b2 i 1 1 1
T = =p = T y: (3.196)
ha2 j b1 i ha2 j b2 i 2 1 1
Then the matrix representation of the operator J^x in the basis (i.e fjb1 i ; jb2 ig =
0
fj+Zi ; j Zig), which we represent by Jx ; becomes
0 1 1 1 ~ 1 0 1 1 1
Jx = T y Jx T = p p
2 1 1 2 0 1 2 1 1
~ 1 1 1 1 ~ 0 1
= =
4 1 1 1 1 2 1 0
0 ^ ^
hb1 j Jx jb1 i hb1 j Jx jb2 i ~ 0 1
) Jx = = (3.197)
hb2 j J^x ja1 i hb2 j J^x jb2 i 2 1 0
3.6 Expectation values using matrices

the average value (expectation value) for an observable A that can be repre-
sented by an operator A^ (e.g. for the measurement of the spin, J^z ) for a particle
(e.g. spin-half particle) in a state
N
X
j i= cn jan i (3.198)
n=1
In chapter one we have shown that the average value for

D the
E measured observable
^ ^
represented by an operator A which we denoted by A is given by
D E XN
^ 2
A = jcn j an = h j A^ j i : (3.199)
n=1
3.6. EXPECTATION VALUES USING MATRICES 81
2
where jcn j is the probability of the particle to be found in the state jan i : One
more time using the completeness relation for the basis fja1 i ; ja2 i ; ::: jaN ig ;
N
X
jan i han j = 1; (3.200)
n=1
we can write
D E N
X N
X N X
X N
A^ = h j jam i ham j A^ jan i han j j i = h j am i ham j A^ jan i han j i :
m=1 n=1 n=1 m=1
(3.201)
For example for two state particle with set of basis fja1 i ; ja2 ig ; one can easily
show that
D E
A^ = h ja1 i h ja2 i ^ ^ : (3.202)
ha2 j A ja1 i ha2 j A ja2 i ha2 j i
or D E
A11 A12 c1
A^ = c1 c2 : (3.203)
A21 A22 c2
where
ha1 j i c1 A11 A12 ha1 j A^ ja1 i ha1 j A^ ja2 i
= ; =
ha2 j i c2 A21 A22 ha2 j A^ ja1 i ha2 j A^ ja2 i
are the matrix representation of the state vector j i and the operator A^ in the
basis vectors fja1 i ; ja2 ig : This can be generalized for any set of complete basis
vectors fja1 i ; ja2 i ; ::: jan ig : It is important to not that the expectation value
would never change with change of basis. This means the expectation value
expressed in terms of this set of basis vectors
D E N X
X N
A^ = h j A^ j i = h j am i ham j A^ jan i han j i : (3.204)
n=1 m=1
can also be expressed, using the completeness relation for another set of basis
vectors fjb1 i ; jb2 i ; ::: jbn ig
N
X
jbn i hbn j = 1; (3.205)
n=1
as
D E N X
X N
A^ = h j A^ j i = h j bm i hbm j A^ jbn i han j i : (3.206)
n=1 m=1
We just simply have three matrices that may have di¤erent elements to multiply
but the …nal result would remain the same. In other words you can use di¤ erent
mechanisms that are not capable of altering the state of the system, you must
get the same value for the measured quantity.
Example 9 For the operator J^z

(a) Find the matrix representation in the J^z basis
(b) Change the matrix representation of J^z from the J^z basis to J^y
D E
(c) Show that the expectation value J^z = 0 using the J^y
Solution:
(a) The matrix representation for J^z is in the J^z basis,
h+Zj J^z j+Zi h+Zj J^z j Zi ~ 1 0

J^z = = ; (3.207)
h Zj J^z j+Zi h Zj J^z j Zi 2 0 1
where we used
~
J^z j Zi = j Zi : (3.208)
2
(b) To change this matrix to Ty basis representation
Jz0 = T y Jz T (3.209)
where T is the transformation matrix that changes the operator J^z from
J^z basis representation to J^y representation which is given by by
h+Z j+Y i h+Z j Y i

T = : (3.210)
h Z j+Y i h Z j Y i
Using
1 i 1 i
j+Y i = p j+Zi + p j Zi ; j Y i = p j+Zi p j Zi
2 2 2 2
one can easily show that
1 1 1 1 1 i
T =p ) Ty = p (3.211)
2 i i 2 1 i
Therefore
1 1 i ~ 1 0 1 1 1
Jz0 = T y Jz T = p p (3.212)
2 1 i 2 0 1 2 i i
~ 0 1
) Jz0 = (3.213)
2 1 0
Then the expectation value
D E 1 ~ 1
0 1 1
) J^z = p 1 i p (3.214)
2 2 1 0 2 i
D E ~ 1
) J^z = i 1 =0
4 i
3.6. EXPECTATION VALUES USING MATRICES 83
Example 10 For the operator J^z2

(a) Find the matrix representation in the J^z basis
(b) Change the matrix representation of J^z2 from the J^z basis to J^y
D E 2
(c) Show that the expectation value J^z2 = ~4 using the J^y
Solution:
(a) The matrix representation for J^z2 is given by
h+Zj J^z2 j+Zi h+Zj J^z2 j Zi

Jz2 = (3.215)
h Zj J^z2 j+Zi h Zj J^z2 j Zi
We note
~ ~
J^z j Zi = j Zi ) J^z2 j Zi = J^z j Zi
2 2
2
~ ~2
) J^z2 j Zi = j Zi = j Zi (3.216)
2 4
so that we …nd for the matrix representation of J^z2 in the S^z basis becomes
~2 h+Z j+Zi h+Z j Zi ~2 1 0
Jz2 = ) Jz2 = : (3.217)
4 h Z j+Zi h Z j Zi 4 0 1
N.B. Since the matrix
1 0
(3.218)
0 1
is an identity matrix you can say the matrix representation of Jz2 in any
2
basis would be the same and the expectation value is just ~4 . But for
the sake of exercise let’s shown it. To change this matrix to Jy basis
representation
Jy
Jz2 ! T y Jz2 T (3.219)
where T is the transformation matrix that changes Jz2 from S^z basis rep-
resentation to S^y representation given by
h+Z j+Y i h+Z j Y i

T = (3.220)
h Z j+Y i h Z j Y i
and T y is the adjoint matrix obtained by transposing and conjugating the

matrix T :
" #
T ra
y h+Z j+Y i h+Z j Y i h+Z j+Y i h Z j+Y i
T = =
h Z j+Y i h Z j Y i h+Z j Y i h Z j Y i
h+Y j+Zi h+Y j Zi
= (3.221)
h Y j+Zi h Y j Zi
Using
1 i
j+Y i = p j+Zi + p j Zi ;
2 2
1 i
j Yi = p j+Zi p j Zi (3.222)
2 2
we …nd
1
h+Z j+Y i = p = h+Z j Y i
2
i i
h Z j+Y i = p ;h Z j Y i = p (3.223)
2 2
so that !
p1 p1 1 1 1
T 2 2 =p (3.224)
pi pi 2 i i
2 2
and
1 1 i
Ty = p (3.225)
2 1 i
Therefore
Jy
Jz2 ! T y Jz2 T (3.226)
becomes
Jy 1 1 i ~2 1 0
Jz2 ! p
2 1 i 4 0 1
1 1 1
p (3.227)
2 i i
Jy ~2 1 i 1 1
) Jz2 ! (3.228)
8 1 i i i
Jy ~2 2 0 ~2 1 0
) Jz2 ! = (3.229)
8 0 2 4 0 1
Then the expectation value

!
~2 1 0 p1
) Jz2 = p1 pi 2
2 2 4 0 1 pi
2
!
~2 p1 ~2
) Jz2 = p1 pi 2 = (3.230)
4 2 2 pi 4
2
3.7. THE POLARIZATION STATE OF A PHOTON 85
3.7 The polarization state of a photon

Light is an electromagnetic wave. Waves can also behave like particles. Photons
are particles of light whose energy is proportional to the frequency of the light
(E=~!) which can be shown by quantization of the electromagnetic wave. We
are not going to do that here. The quantum description of light is signi…cant
when we deal with small number of photons. What we are going to do here
is applying what we have studied for spin- 12 particles to describe the state of
polarization of light. The polarization of light is determined by the electric
~
…eld, E:The interaction of light with matter, in most cases, is electrical and
therefore we shall focus on only the electric …eld. We consider a plane EM
waves propagating along the positive z-direction. The electric …eld of such EM
wave can be described the wave equation
~ = (E0x x
E ^ + E0y y^) ei(kz !t)
; (3.231)
where k is the wave number, ! is the angular frequency, E0x and E0y are the
amplitude of the electric …eld in the x and y; direction, respectively, which are
complex in general that can be expressed as
E0x = jE0x j ei x ; E0y = jE0y j ei y : (3.232)
Suppose we set x = 0 and measure y = relative to x; then we can write
~ = jE0x j ei(kz
E !t)
^ + jE0y j ei(kz
x !t+ )
y^: (3.233)
The polarization state of light is de…ned by the value of the phase angle :
Linearly Polarized : when the phase di¤erence between the x and y compo-
nent of the electric …eld, = 0, the electric …eld becomes
~ = (jE0x j x
E ^ + jE0y j y^) ei(kz !t)
and the light is linearly polarized. Under this condition if jE0y j = 0 the light is
x-polarized; and if jE0x j = 0; the light is y-polarized.
Elliptically polarized : when the phase di¤erence is = =2; the electric
…eld becomes
~ = jE0x j ei(kz
E !t)
^ + jE0y j ei(kz
x !t 2 ) y^ = (jE j x
0x ^ i jE0y j y^) ei(kz !t)
(3.234)
Circularly polarized : when the phase di¤erence is = =2; and also jE0x j =
jE0y j = E0 ; the electric …eld becomes
~ = E0 ei(kz
E !t)
^ + E0 ei(kz
x !t 2 ) y^ = (E x
0^ iE0 y^) ei(kz !t)
: (3.235)
~ : Therefore, for a circularly po-

In reality the electric …eld is given by Re E
Figure 3.2: Linearly, circularly, and elliptically polarized wave.
larized light we may write
~ = Re [(E0 x
Re E ^ iE0 y^) (cos (kz !t) + i sin (kz !t))]
~ = Re [(E0 x
) Re E ^ iE0 y^) (cos (kz !t) + i sin (kz !t))]
~ = E0 cos (kz
) Re E !t) x
^ E0 y^ sin (kz !t) (3.236)
For = =2; we …nd
~ = E0 cos (kz
Re E !t) x
^ E0 y^ sin (kz !t) (3.237)
and = =2
~ = E0 cos (kz
Re E !t) x
^ + E0 y^ sin (kz !t) : (3.238)
Now let’s see how the electric …eld evolves with time at z = 0: For = =2
~ = E0 cos ( !t) x
Re E ^ E0 y^ sin ( !t) = E0 cos (!t) x
^ +E0 y^ sin (!t) (3.239)
This means that, as shown in the …gure below the electric …eld rotates from the
positive x-axis to the positive y axis. This means if we curl right hand from the
x axis to the y axis our thumb points in the direction of propagation which is
the positive axis, and it is known as right-circularly polarizedOn the other hand
for = =2
~ = E0 cos ( !t) x
Re E ^ +E0 y^ sin ( !t) = E0 cos (!t) x
^ E0 y^ sin (!t) (3.240)
and the electric …eld rotates from the positive x axis towards the negative y
axis. This means if we put our left hand and curl it from positive x to negative
y our thumb points in the direction of propagation of the light, and the light is
called left-circularly polarized light.
3.7. THE POLARIZATION STATE OF A PHOTON 87
Now going back to our complex representation of the electric …eld we can
describe the states of polarization of light as
E~ = jE0x j x
^ + jE0y j y^ linearly polarized
~
E = jE0x j x
^ + i jE0y j y^ right-eliptically polarized
~ = jE0x j x
E ^ i jE0y j y^ left-eliptically polarized
~ = jE0 j (^
E x + i^
y) right-circularly polarized
~ = jE0 j (^
E x i^
y) left-circularly polarized (3.241)
Let’s consider a photon with a unit magnitude of electric …eld and same mag-
nitude in the x and y direction. Let the phase angle be = 4 and represent
x polarization by the ket vector jXi and y polarization by the ket vector jY i,
then one can write state for a right- and left-circularly polarized photons as
1
jRi = p (jXi + i jY i) , right-circularly polarized
2
1
jLi = p (jXi i jY i) ; left-circularly polarized. (3.242)
2
The basis vectors jXi and jY i are orthonormal
hX jY i = hY jXi = 0; (3.243)
as y-polarized photons can not pass through a Polaroid with a transmission axis
along the x direction and x-polarized photons can not pass through a Polaroid
with a transmission axis along the y direction. Further more
hY jY i = hX jXi = 1; (3.244)
for an ideal polaroid with a transmission axis along the x-direction can pass all
x polarized photons and the same is true for y polarized photons. Therefore,
the basis jXi and jY i form a complete set
jXi hXj + jY i hY j = 1 (3.245)

3.8 Birefregent crystals-like SG apparatus for

photons
Birefringence is the optical property of a crystal having a refractive index that
depends on the polarization and propagation direction of light. Such crystals
are described by their optic axis. An optic axis of a crystal is the direction in
which a ray of transmitted light su¤ers no birefringence. Suppose a linearly
polarized light is incident on a birefregent crystal as shown in Fig.3.3 For a
Figure 3.3: A linearly polarized photon propagating in the z-direction incident

on a birefregent crystal.
linearly polarized incident photon, one can write
x + y^) ei( c nz !t)

!
~ = (^
E x + y^) ei(kz !t)
= (^ (3.246)
where we used
! c 2 !
v= ;v = ;k = ) k = n: (3.247)
2 n c
Now if the optic axis is parallel to the x–axis, the x-component of the electric
…eld su¤ers no birefringence. However, the y component of the electric …eld
does, after the photon traverses the crystal, there will be a phase di¤erence
between the x and y components of the electric …eld
! ! !
'= ny l !t nx l !t = (ny nx ) l (3.248)
c c c
If the crystal is designed in such a way that
!
'= (ny nx ) l = ; (3.249)
c 2
3.8. BIREFREGENT CRYSTALS-LIKE SG APPARATUS FOR PHOTONS89
the transmitted light becomes circularly polarized light. If one chooses the
refractive index along x and y of the crystal such that
ny nx = 1 (3.250)
we …nd
! 2 0
l= ) l= )l= ; (3.251)
c 2 0 2 4
it shows the crystal length should be a quarter of the wave length of the incident
photon in free space (or air) and such plates are called quarter-wave plates. If
we want to rotate a linearly polarized photon an angle without any phase
delay between the x and y components of the electric …eld, we must have
!
' = (ny nx ) l = ; (3.252)
c
so that the electric …eld for a linearly polarized light incident on the crystal
~ = jE0x j ei(kz !t) x
E ^ + jE0y j ei(kz !t) y^: (3.253)
when exiting the crystal still remains linearly polarized but rotated by and angle
~ = jE0x j ei(kz
E !t+ )
^ + jE0y j ei(kz
x !t+ ) ~
y^ = ei E: (3.254)
Thus for
ny nx = 1 (3.255)
we …nd
! 2 0
l= ) l= )l= ; (3.256)
c 0 2
such plates are called half-wave plates and are used to rotate the polarization
direction of an already linearly polarized photons.
Suppose we rotate a circularly polarized photon in the state jRi by an angle
', such that the photon will have a state
^ ('^ 1
jR0 i = R z ) jRi = p (jX 0 i + i jY 0 i) :
2
^
where R ('^ z ) is an operator describing the action we took to rotate the polariza-
tion state of the photon. This action like in the case of spin-half particle where
we send the particle through the SG apparatus, here we can think of sending the
photon through birefringent crystal of some speci…ed thickness that determines
the phase di¤erence between the x and y components of the electric …eld.
From Fig. ??, one can easily see that
^ ('^
jR0 i = R z ) jRi = cos ' + jXi + sin ' + i jY i
2 2
^ ('^ 1
) jR0 i = R z ) jRi = p [[cos (') sin (')] jXi + [cos (') + sin (')] i] jY i
2
1 1
) jR0 i = p [cos (') jXi + sin (') i jY i] + p [ sin (') jXi + cos (') i jY i]
2 2
0 ^ ('^ 1
jR i = R z ) jRi = p [jX 0 i + jY 0 i] : (3.257)
2
where
jX 0 i = cos (') jXi + sin (') i jY i ; jY 0 i = sin (') jXi + cos (') i jY i (3.258)
which is the rotation of the coordinates described by jXi ; jY i to a new coordi-

nate described by jX 0 i ; jY 0 i by an angle ' about the z–axis in a counterclockwise
direction. Therefore, we note that
^ ('^
jR0 i = R z ) jRi = e i'
jRi : (3.259)
Comparing this result with what we found for spin-half particles when the spine
is rotated by 2 ; the state is rotated by 4
^ 1
R j j+Zi = p (j+Zi + j Zi) = j+Xi
2 2
^ ' '
) R ('j) j+Zi = cos j+Zi + cos j Zi : (3.260)
2 2
In such cases, where the spin is rotated by ' the state is rotated by '=2; we
had for the rotation generator operator
~
J^z j Zi = j Zi :
2
Similarly, one can then make the argument that spin-1 particles like the photon
where the spin is rotated by ' the state is rotated by '; we must have
^ ^
^ ('^ i J~z ' ^ ('^ i J~z ' i'
R z) = e )R z ) jRi = e jRi = e jRi
^
^ ('^ i J~z ' i'
R z ) jLi = e jLi = e jRi (3.261)
and
J^z jRi = ~ jRi ; J^z jLi = ~ jLi :
3.8. BIREFREGENT CRYSTALS-LIKE SG APPARATUS FOR PHOTONS91
Figure 3.4: A real polarizer with transmission axis rotated by an angle, '; in a
counterclockwise direction.
Example 11 Suppose the transmission axis of a polaroid represented by the

ket vector jX 0 i is rotated by ' counterclockwise about the z-axis as shown
in the …gure below. The complete absorption direction of the polaroid
represented by jY 0 i is normal to jX 0 i : Express these vectors in jXi and
jY i basis and determine the transformation matrix that changes the state
of a photon expressed as
0
= c0x jX 0 i + c0y jY i :
to
0
= cx jXi + cy jY i
Solution: Using the completeness relation, we can write
jX 0 i = (jXi hXj + jY i hY j) jX 0 i ; jY 0 i = (jXi hXj + jY i hY j) jY 0 i (3.262)
jX 0 i = jXi hXj X 0 i + jY i hY j X 0 i ; jY 0 i = jXi hXj Y 0 i + jY i hY j Y 0 i

(3.263)
jX 0 i = cos (') jXi + sin (') jY i ;

jY 0 i = cos + ' jXi + sin + ' jY i = sin (') jXi + cos (')
(3.264)
jY i :
2 2
Once again using the completeness relations we can write
0
= (jXi hXj + jY i hY j) c0x jX 0 i + c0y jY 0 i
= c0x (hXj X 0 i jXi + hY j X 0 i jY i) + c0y (hXj Y 0 i jXi + hY j Y 0 i jY i)
= c0x (cos (') jXi + sin (') jY i) + c0y ( sin (') jXi + cos (') jY i)
= c0x cos (') c0y sin (') jXi + c0x sin (') jXi + c0y cos (') jY i :
For
0
= cx jXi + cy jY i
then one can write
cx = c0x cos (') c0y sin (') ; cy = c0x sin (') jXi + c0y cos (')
which can be put in a matrix form as
cx cos (') sin (') c0x

= : (3.265)
cy sin (') cos (') c0y
Thus the transformation matrix T becomes

cos (') sin (') hXj X 0 i hXj Y 0 i
T = =
sin (') cos (') hY j X 0 i hY j Y 0 i
hXj R^ ('^z ) jXi hXj R ^ ('^
z ) jY i
) T = ^ ^ (3.266)
hY j R ('^z ) jXi hY j R ('^z ) jY i
where we expressed R ^ ('^

z ) is the rotation about the z axis in a counter-
clockwise direction by an angle ':
Chapter 4
Angular Momentum
In quantum mechanical description of the angular momentum, the relationship

of the operators describing the components is important. In this chapter we
shall focus on these relationships and the eigen values and eigen vectors of the
total and the components of the angular momentum operators.
4.1 Commutation relations for the rotation op-

erators
Whether it is orbital angular momentum operator or intrinsic spin angular mo-
mentum it involves a rotation operation. In quantum mechanics the order of
rotation when we make two or more successive rotations makes a very big dif-
ference. As a matter of fact even in classical description, order of rotations
do make a di¤erence. As an example let’s consider person shown in Fig. 4.1.
Suppose somebody rotated this person about the positive x-axis in a counter
clockwise direction by an angle of =2 and then by the same angle about the
z-axis in the same direction.
Figure 4.1: A rotation about the y–axis and then a rotation about the z-axis.
93
94 CHAPTER 4. ANGULAR MOMENTUM
Figure 4.2: A rotation about the z–axis and then a rotation about the y-axis.
This same person positioned at the same place is rotated in the reverse order.
First about the z-axis and then about the y-axis as shown in Fig. 4.2. We can
clearly see that the …nal positions for the parts of this person’s body in these
two di¤erent order of rotations are di¤erent. Therefore, the order of rotation
do make a di¤erence in the …nal outcome. If we use our quantum description
^ ('k) for a rotation about the z-axis, R
for these rotation operation,R ^ ('j) for a
rotation about the y-axis, and the state (the position state in this case) by j i ;
what we have just observed is that
^ ('k) R
R ^ ('j) j i = ^ ('j) R
6 R ^ ('k) j i ) R
^ ('k) R
^ ('j) 6= R
^ ('j) R
^ ('k) :
This indicates that the rotation operators describing rotations about di¤erent
axes do not commute. So the question is the what is the relationship for two
reversely ordered rotations about an axis
^ ('k) R
R ^ ('j) ^ ('j) R
R ^ ('k) = ?;
^ ('i) R
R ^ ('j) R^ ('j) R
^ ('i) = ?;
^ ('i) R
R ^ ('k) ^ ('k) R
R ^ ('i) = ?:
Next we shall determine these commutation relations for the components of the
rotation operator. We will use this relation to determine commutation relations
for the rotation generator operators (angular momentum or spin operators).
In quantum mechanics, generally, as we have already seen that a physical
process described by operator, O.^ When a system undergoes through this phys-
ical process its state, j i changes to a di¤erent state 0 as we have observed
in the spin-half particles passing through the SG apparatus,
^j i=
O 0
: (4.1)
So basically the physical process changes the vector j i to another vector 0
in the Hilbert space. In the case of the rotation operator, for example for a
rotation about the z-axis, we have
^ ('k) j i =
R 0
(4.2)
4.1. COMMUTATION RELATIONS FOR THE ROTATION OPERATORS95
which shows the state vector j i is rotated to a new state 0 in Hilbert space:
To establish the relationship between these two vectors and then determine
the matrix representation of the rotation operator in some basis, let’s consider a
rotation of a vector in real space. We have seen in chapter 1 the rotation of the
coordinate system but this time we rotate the vector instead of the coordinate
system because that is what a rotation operator does to the state vector.
Suppose we rotated the vector A ~ = (Ax ; Ay ; Az ) by an angle ' about the
z-axis and found a new vector A ~ = A0x ; A0y ; A0z : The projection of the vector
0
~ on the x-y plane makes an angle from the positive x-axis as shown in
A
Fig.4.1.Then one can easily express the components of the new vector A ~0 =
A0x ; A0y ; A0z as
A ~ ) A02
~0 = A 02 02 2 2 2
x + Ay + Az = Ax + Ay + Az : (4.3)
The rotation about the z-axis, as one can see from Fig. 4.1, does not change
the z-componet of the vector,
A0z = Az : (4.4)
which leads to
A02 02 2 2
x + Ay = Ax + Ay : (4.5)
~0
Then, referring to Fig. 4.1 for the x and y components of A ; one can write
q q
A0y = A02 02
x + Ay sin ( + ') = A2x + A2y sin ( + ')
q q
) A0y = A2x + A2y sin ( ) cos (') + A2x + A2y cos ( ) sin (') ; (4.6)
and
q q
A0x = A02 02
x + Ay cos ( + ') = A2x + A2y cos ( + ')
q q
) A0x = A2x + A2y cos ( ) cos (') A2x + A2y sin ( ) sin (') : (4.7)
From Fig. 4.1, we note that

q q
Ay = A2x + A2y sin ( ) ; Ax = A2x + A2y cos ( ) (4.8)
and one can then write for the components of the rotated vector
A0x = Ax cos (') Ay sin (') ; A0y = Ax sin (') + Ay cos (') ; A0z = Az : (4.9)
which can be put in using matrices as

2 32 3 2 0 3
cos (') sin (') 0 Ax Ax
4 sin (') cos (') 0 5 4 Ay 5 = 4 A0y 5 : (4.10)
0 0 1 Az A0z
Now let’s go back to our rotation of the state vector in Hilbert space. Suppose a
~ and results another
state vector j i is rotated in the same way like the vector A
state vector 0 as shown in Fig. 4.3. We describe this using the rotation
Figure 4.3: A rotated state vector in Hilber space.
^ ('k)
operator R
^ ('k) j i =
R 0
(4.11)
one can write the matrix representation in terms of a complete basis set of
vectorfja1 i ; ja2 i ; ja3 ig ;
2 ^ ('k) ja1 i ha1 j R ^ ('k) ja3 i 3 2 c1 3 2 c0 3
^ ('k) ja2 i ha1 j R
ha1 j R 1
4 ha2 j R^ ('k) ja1 i ha2 j R ^ ('k) ja3 i 5 4 c2 5 = 4 c02 5
ha3 j R ^ ('k) ja2 i ha3 j R
^ ('k) ja3 i c3 c03
(4.12)
where 2 3 2 0 3
c1 c1
j i ! 4 c2 5 ; 0 ! 4 c02 5 : (4.13)
c3 c03
Therefore, comparing Eqs. (4.10) and (4.12) one can easily see that
2 3
cos (') sin (') 0
R ('k) = 4 sin (') cos (') 0 5 (4.14)
0 0 1
^ ('k) : Following a sim-
is the matrix representation for the rotation operator, R
ilar procedure one can easily show that for a rotation by an angle ' in a coun-
terclockwise direction about the x and y axis, are given by
2 3
1 0 0
R ('i) = 4 0 cos (') sin (') 5 (4.15)
0 sin (') cos (')
and 2 3
cos (') 0 sin (')
R ('j) = 4 0 1 0 5; (4.16)
sin (') 0 cos (')
respectively.
For a small angle rotation by ' << 1; keeping only the lowest order in-
volving ' in the Taylor series expansion for the sin and cos functions, we
have
2
( ')
cos ( ') = 1 ; sin ( ') = ' (4.17)
2
so that the matrix representation for the rotations about the x, y, and z axes
by an angle ' become
2 3
1 0 0
6 2 7
R ( 'i) = 4 0 1 ( 2') ' 5; (4.18)
2
( ')
0 ' 1 2
2 3
( ')2
1 2 0 '
6 7
R ( 'j) = 4 0 1 0 5; (4.19)
2
' 0 1 ( 2')
2 2
3
1 ( 2') ' 0
6 2 7
R ( 'k) = 4 ' 1 ( 2') 0 5: (4.20)
0 0 1
Let’s do the rotations we discussed in Fig. 4.1 and 4.2. But these time the
rotation about each axes is by small angle ' instead of by =2: For a rotation
about the y axis followed by about the z-axis in a counterclockwise directions
by an angle ', we have.
R ( 'j) R ( 'k)
2 2
32 2
3
1 ( 2') 0 ' 1 ( 2') ' 0
6 76 2 7
= 4 0 1 0
2
54 ' 1 ( 2') 0 5
' 0 1 ( 2') 0 0 1
2 2 2 2
3
1 ( 2') 1 ( 2') ' '
6 7
6
= 4 ' 1 ( ') 2
0 7: (4.21)
2 5
2 2
( ') 2 ( ')
1 2 ' ( ') 1 2
and for the reverse order rotation
R ( 'k) R ( 'j)
2 2
32 3
( ')2
1 ( 2') ' 0 1 2 0 '
6 2 76 7
= 4 ' 1 ( 2') 0 54 0 1 0
2
5
( ')
0 0 1 ' 0 1 2
2 2 2 3
( ')2
1 ( 2') ' ' 1 2
6 7
= 6
4 ' 1
( ')2
1 ( ')2
( ')
2 7:
5 (4.22)
2 2
( ')2
' 0 1 2
There follows that
R ( 'j) R ( 'k) R ( 'k) R ( 'j)

2 2 2 3
( ') ( ')2
1 2 1 2 ' '
6 7
=6
4 ' 1 ( ')2
0 7
5
2
( ')2 2 ( ')2
1 2 ' ( ') 1 2
2 2 3
( ')2 ( ')2
1 2 ' ' 1 2
6 7
6 ( ')2 ( ')2 2 7
4 ' 1 2 1 2 ( ') 5
( ')2
' 0 1 2
2 ( ')3 ( ')3
3
0 2 2
6 ( ')3 2 7
=4 2 0 ( ') 5 (4.23)
( ')3 2
2 ( ') 0
3
Since we can make our rotation as small as we want to, we can set ( ') ' 0:
This leads to
2 3
0 0 0
2
R ( 'j) R ( 'k) R ( 'k) R ( 'j) = 4 0 0 ( ') 5
2
0 ( ') 0
2 3 2 3
1 0 0 1 0 0
2
=4 0 1 ( ') 5 4 0 1 0 5 (4.24)
2
0 ( ') 1 0 0 1
2
Suppose if one make a rotation by an angle of '0 = ( ') ; in a counterclock-
wise direction about the x axis, the rotation matrix for such a rotation can be
written as
2 3
1 0 0
6 2 2 7
R ( ') i = 6 0 cos ( ') sin ( ') 7
2
4 5
2 2
0 sin ( ') cos ( ')
2 3 2 3
1 0 0 1 0 0
6 4
2 7 2
' 4 0 1 ( 2') ( ') 5 ' 4 0 1 ( ') 5
2 ( ')4 2
0 ( ') 1 2
0 ( ') 1
2 3 2 3
0 0 0 1 0 0
2
=4 0 0 ( ') 5 + 4 0 1 0 5
2
0 ( ') 0 0 0 1
2 3
0 0 0
2
)4 0 0 ( ') 5 = R ( ')2 i I: (4.25)
2
0 ( ') 0
One can then rewrite the commutation relation for the matrix representation
for the components of the rotation operators as
2
R ( 'j) R ( 'k) R ( 'k) R ( 'j) = R ( ') i I: (4.26)
that can be put in terms of the corresponding operators in the form

^ ( 'j) R
R ^ ( 'k) ^ ( 'k) R
R ^ ( ')2 i
^ ( 'j) = R ^
I: (4.27)
Using the rotation generators we recall that these operators (for spin-one par-
ticles like a photon) can be expressed as
!2
^
J^
i ~y ' ^ J^y 1 J^y
R ( 'j) = e =I i '+ ' :::;
~ 2 ~
!2
^
^
i J~z ' ^ J^z 1 J^z
R ( 'k) = e =I i '+ ' :::;
~ 2 ~
^ ( ')2 i
^
i J~x ( ')2 J^x 2
R = e = I^ i ( ') :::; (4.28)
~
so that the commutation relation becomes

2 !2 3 2 !2 3
^ ^ ^ ^
4I^ i Jy ' + 1 Jy
' :::5 4I^ i
Jz
'+
1 Jz
' :::5
~ 2 ~ ~ 2 ~
2 !2 3 2 !2 3
^ ^ ^ ^
4I^ i Jz ' + 1 Jz
' :::5 4I^ i
Jy
'+
1 Jy
' :::5
~ 2 ~ ~ 2 ~
J^x 2
= i ( ') : (4.29)
~
The zero and …rst order in ' cancel out and keeping only up to the second
order in ' on the left side of this equation, one can easily …nd
" #" # " #" #
J^y J^z J^z J^y
i ' i ' i ' i '
~ ~ ~ ~
J^x 2
= i ( ') ) J^y J^z J^z J^y = i~J^x :
~
Therefore the commutation relation for the components to the rotation genera-
tors become h i
J^y ; J^z = J^y J^z J^z J^y = i~J^x
in a similar way one can verify that
h i h i
J^z ; J^x = i~J^y ; J^x ; J^y = i~J^z
which is one of your homework problem.
4.2 None commuting operators and the uncer-

tainty principle
We have proved that the operators representing the di¤erent components of
the angular momentum (Rotation generator operators) of a particle do not
commute. The commutation relation between the three components are given
by h i h i h i
J^x ; J^y = i~J^z ; J^y ; J^z = i~J^x ; J^z ; J^x = i~J^y : (4.30)
The question one may ask could be "So what???, What is the big deal?". Well,
we going to see that it is really a big deal in quantum mechanics as it has a very
signi…cant physical consequences. Next we shall see this physical signi…cance
more generally rather than to angular momentum operators..
Let’s consider two operators A^ and B ^ representing some two physical ob-
servables that do not commute. Suppose the commutation relation for these
operators is given by h i
^ B
A; ^ = iC:^ (4.31)
4.2. NONE COMMUTING OPERATORS AND THE UNCERTAINTY PRINCIPLE101
We recall that operators representing physical observables are Hermitian

D E D E D E D E
A^ = A^y ; B
^=B^ y ) A^ = A^ ; B ^ = B ^ : (4.32)
Let the particle be in a state described by the ket vector j i : We recall from
Chapter one, the uncertainty (Standard deviation) in the measurement of these
observables are given by
D E D E2 D E D E2
2 2
( A) = A^2 A^ ; ( B) = B
^2 ^ ;
B (4.33)
where D E D E
A^2 = h j A^2 j i =; A^ = h j A^ j i ; h j i = 1; (4.34)
and D E D E
^2 = h j B
B ^ 2 j i =; B
^ = h jB
^ j i ; h j i = 1: (4.35)
There follows that

D E D E2 D E D E2
2 2
( A) ( B) = A^2 A^ ^2
B ^
B (4.36)
Noting that
D E2 D E D E
A^ = h j A^ j i h j A^ j i = h j A^ j i A^ = h j A^ A^ j i ;
D E2 D E D E
B^ = h jB ^ j ih jB ^ j i = h jB ^j i B ^ =h j B ^ B ^ j i (4.37)
we have
D E D E
2 2
( A) ( B) = h j A^2 j i h j A^ A^ j i ^2 j i
h jB ^ B
h j B ^j i
(4.38)
so that one can write
D E D E
2 2
( A) ( B) = h j A^ A^ A^ j i h jB ^
^ B ^ j i :
B (4.39)
Noting that
D E D E D E D E
h j A^ A^ A^ j i = h j A^ A^ + A^ A^ A^ j i
D E 2 D E D E
= h j A^ A^ j i + h j A^ A^ A^ j i
D E 2 D E D E2
= h j A^ A^ j i + A^ h j A^ j i h j A^ j i
D E 2 D E2 D E2
= h j A^ A^ j i + A^ A^
D E D E 2
) h j A^ A^ A^ j i = h j A^ A^ j i; (4.40)
and similarly
D E D E 2
^ B
h jB ^ ^ j i=h j B
B ^ ^
B j i
one can write

D E 2 D E 2
2 2
( A) ( B) = h j A^ A^ ^
j ih j B ^
B j i: (4.41)
Introducing the ket vectors de…ned by

D E D E
j i = A^ A^ j i ; j i = B
^ ^ j i
B
one can write the corresponding bra vectors

D E D E
h j = h j A^y A^ = h j A^ A^ ;
D E D E
h j = h j B ^y B^ =h j B^ ^ ;
B
where we used Hermiticity of operators representing a physical observable,

D E D E D E D E
^=B
B ^y ) B ^ = B ^ ; A^y = A^ ) A^ = A^ :
Then in terms of these ket vectors, we may write the uncertainty in the two
none commuting operators as
2 2
( A) ( B) = h j i h j i : (4.42)
Next we will establish one important inequality know as Schwartz inequality.

To this end, let’s consider two vectors, ~ and ~ ; in a complex vector space as
shown in Fig. Let the angle between these two vectors be ; then one can write
2
2
j~ j = ~ ~ 0; ~ =~ ~ 0;
2
~ 2
~ ~ ~ = j~ j ~ cos ( ) j~ j ~ cos ( ) = j~ j ~ cos2 ( ) (4.43)
0:
There follows that

2 2
2 2
j~ j ~ j~ j ~ cos2 ( ) = j~ j ~ cos ( ) j~ j ~ cos ( ) (4.44)
and using Dirac notation this can be put in the form

2
h j ih j i h j i h j i = jh j ij : (4.45)
This is known as Schwartz inequality. Using the Schwartz inequality, one can
then write
2 2 2
( A) ( B) jh j ij : (4.46)
4.2. NONE COMMUTING OPERATORS AND THE UNCERTAINTY PRINCIPLE103
Figure 4.4: Two vectors in a complex vector space.
Now going back to the explicit form of these ket vectors

D E D E
j i = A^ A^ j i ; j i = B ^ B^ j i (4.47)
we have
D E D E 2
2 2 2
( A) ( B) jh j ij = h j A^ A^ ^
B ^ j i :
B (4.48)
^ one can write

For any operator O;
0 1
^ y ^ i ^y O
O ^
^ = O + O + i@
O A=O
^=a
^1 + i^
a2 ; (4.49)
2 2
where
^y + O
^ ^y O
i O ^
O
a
^1 = ;a
^2 = ; (4.50)
2 2
are Hermitian operators and known as Quadrature operators (in quantum op-
tics). Noting that
D E D E D E y D E y
^ = A^
O A^ ^
B ^
B )O^y = B ^ B^ A^ A^
D E D E
^y = B
)O ^ ^
B A^ A^ (4.51)
we …nd h i
^y
i O ^
O ^ A^
i B A^B
^ ^ B
i A; ^
C^
a
^2 = = = = ; (4.52)
2 2 2 2
so that we may write
D E D E C^
^ = A^
O A^ ^
B ^
B =a
^1 + i (4.53)
2
Note that we have used the commutation relation
h i
^ B
A; ^ = iC:
^ (4.54)
Thus one can write

! 2
D E D E 2 C^
2 2
( A) ( B) h j A^ A^ ^
B ^ j i
B = h j a
^1 + i j i
2
! !
C^ C^ i D Ê i D Ê
=h j a
^1 + i j ih j a
^1 i j i = h^
a1 i + C h^
a1 i C
2 2 2 2
2 2 2 1 D ^ E2
( A) ( B) h^
a1 i + C : (4.55)
4
^1 and C^ are Hermitian operators, obviously

Since a
D E 1 D ^ E2 1 D ^ E2
2 2
h^
a1 i 0; C^ 0 ) h^
a1 i + C C ; (4.56)
4 4
Therefore, we can write the uncertainty relation
2 2 1 D ^ E2
( A) ( B) C (4.57)
4
where the two operators A^ and B

^ obeys the commutation relation
h i
^ B
A; ^ = iC:
^ (4.58)
Note that both operators A^ and B

^ (also C)
^ must be Hermitian operators.
Example 4.1 Find the uncertainity relations for components of the angular
momentum where the operators obey the commutations relation
h i
J^x ; J^y = i~J^z (4.59)
Solution: Let’s consider the components of the angular momentum operators.

We recall the commutation relations are found to be
h i h i h i
J^x ; J^y = i~J^z ; J^y ; J^z = i~J^x ; J^z ; J^x = i~J^y ; (4.60)
4.3. COMMUTING OPERATORS AND THE EIGENSTATES 105
for A^ = J^x and B

^ = J^y ; we have
h i
J^x ; J^y = i~J^z ) C^ = ~J^z (4.61)
so that
2 2 ~2 D ^ E2 ~DÊ
( Jx ) ( Jy ) Jz ) ( Jx ) ( Jy ) Jz : (4.62)
4 2
Example 4.2 For position and momentum, you were introduced in modern
physics the commutation relation is given by
[^
x; p^x ] = i~; (4.63)
show that the uncertainty relation is given by

~
( x) ( px ) : (4.64)
2
where x^ and p^x are the position and momentum operator, respectively,
for one dimensional case.
Solution: For A^ = x
^ and B^ = p^x are the position and momentum operator for
one dimensional case, respectively. For this commutation the uncertainty
relation
2 2 1 D ^ E2
( A) ( B) C (4.65)
4
becomes
2 2 ~2 ~
( x) ( px ) ) ( x) ( px ) ; (4.66)
4 2
which is the Heisenberg uncertainty principle.
4.3 Commuting operators and the eigenstates

Simultaneous eigenstate can be determined for two or more operators that com-
mutes. We can show this by considering two cases one when the eigenstates are
degenerate (have the same eigenvalue) and when it is not.
None Degenerate Case: Suppose the operator A^ commutes with operator B ^
h i
^ B
A; ^ =0 (4.67)
and has a nondegenerate eigenstate jua i with a corresponding eigenvalue a
A^ jua i = a jua i : (4.68)

^ acts on this eigenvalue equation
when the operator B
^ A^ jua i = aB
B ^ jua i : (4.69)
when the two operators commute, we have

h i
^ B
A; ^ =0)B ^ A^ = A^B
^ (4.70)
so that
A^ B
^ jua i = a B
^ jua i : (4.71)
This means that the ket vector

^ jua i
jvb i = B (4.72)
is the eigen state of the operator A,^ with eigenvalue a. This can be true if an
only if
^ jua i = b jua i
jvb i = B (4.73)
in order to satisfy the equation
A^ B
^ jua i = a B
^ jua i ) A^ (b jua i) = a (b jua i)
) A^ jua i = a jua i : (4.74)
Therefore, we can conclude that two commuting operators A^ and B

^ have a
simultaneous eigenstate which we denote as jvab i such that
A^ jvab i = a jvab i ; B
^ jvab i = b jvab i : (4.75)
Degenerate Case: Suppose the operator A^ commutes with operator B

^
h i
^ B
A; ^ =0 (4.76)
E E
(1) (2)
and has two degenerate eigenstates ua and ua with the same eigenvalue
a; E E
A^ u(1)
a = a u(1)
a (4.77)
E E
A^ u(2)
a = a u(2)
a : (4.78)
Upon adding these two eigenstates we have

E E E E
A^ u(1)
a + u(2)
a = a u(1)
a + u(2)
a (4.79)
and upon subtracting

E E E E
A^ u(1)
a u(2)
a =a u(1)
a u(2)
a : (4.80)
This suggest that the linear combination of the two degenerate eigenstates are
also the eigenstates for the operator A^ with eigenvalue a. Therefore we may
4.3. COMMUTING OPERATORS AND THE EIGENSTATES 107
de…ne two eigen states which are the linear combination of these two degenerate
eigen states as
E E E E E E
va(1) = u(1)
a + u(2)
a ; v (2)
a = u(1)
a u(2)
a (4.81)
such that E E E E
A^ va(1) = a va(1) ; A^ va(2) = a va(2) : (4.82)
^ acting on these eigenstates, we have

For an operator B
E E E E
B ^ A^ v (2) = aB
^ v (1) ; B
^ A^ v (1) = aB ^ v (2)
(4.83)
a a a a
when the two operators commute, we have

h i
^ B
A; ^ =0)B ^ A^ = A^B
^ (4.84)
so that
E E E E
^ va(1)
A^ B ^ va(1)
=a B ^ va(2)
; A^ B ^ va(2)
=a B (4.85)
These two equations mean that the eigenstates

E E E E
^ v (1) ; v 0(2) = Bv
va0(1) = B ^ v (2) (4.86)
a a a
^ with eigenvalue a. Again this can be true

are the eigenstates of the operator A,
when E E E E
B^ va(1) = b1 v (1) ; B
^ v (2) = b2 v (2) (4.87)
a a a
so that
E E E E
^ va(1)
A^ B ^ va(1)
=a B ) A^ b1 va(1) = a b1 va(1)
E E
) A^ va(1) = a va(1) : (4.88)
E E E E
A^ B
^ v (2)
a
^ v (2)
=a B a ) A^ b2 va(2) = a b2 va(2)
E E
) A^ va(2) = a va(2) : (4.89)
Therefore, we can conclude that two commuting operators A^ and B

^ have a
simultaneous eigen state which we denote as jvab i such that
A^ jvab i = a jvab i ; B
^ jvab i = b jvab i : (4.90)
The converse is also true! That means if two operators have the same
eigenstate, the two operators must also commute. Suppose the eigenstate juab i
is the eigenstate to two di¤erent observable described by the operators A^ and

B^ such that
A^ juab i = a juab i ; B
^ juab i = b juab i : (4.91)
then we have
^ A^ juab i = aB
B ^ juab i = ab juab i ; A^B
^ juab i = bA^ juab i = ab juab i : (4.92)
so that h i
A^B
^ ^ A^ juab i = 0 ) A^B
B ^ ^ A^ = 0 ) A;
B ^ B
^ : (4.93)
This proves that that if two operators A^ and B

^ have simultaneous eigenstates,
then the two operators must commute
4.4 Angular momentum eigenvalue equation

Since J^ and J^z form a commuting set of operators, one can determine a simul-
taneous eigenstate,jj; mi ; satisfying the eigenvalue equations
J^2 j ; mi = ~2 j ; mi ; J^z j ; mi = ~m j ; mi ; (4.94)
where
J^2 = J^x2 + J^y2 + J^z2 ; j ; mi = j i jmi ; (4.95)
Note that J^2 acts on j i and J^z on jmi : In order to solve this eigenvalue equa-
tions and determine the eigenvalues and the eigenstates, we introduce two im-
portant none Hermitian operators de…ned by
J^+ = J^x + iJ^y ; J^ = J^x iJ^y (4.96)
with
y
J^+ = J^ ; J^+ = J^y : (4.97)
The operator J^+ J^ are called the raising (lowering) operators. The name and
the importance of these operators in solving the angular momentum eigenvalue
equation originates from its commutation relation with J^z and what it does to
the eigenstate j ; mi :
Commutation properties of the Raising and Lowering operators: The com-
mutation between the raising and lowering operators can be written as
h i h i h i h i
J^+ ; J^ = J^x + iJ^y ; J^x iJ^y = i J^x ; J^y + i J^y ; J^x (4.98)
which leads to h i
J^+ ; J^ = 2~J^z (4.99)
We note that the commutator of J^z and J^ is

h i h i
J^z ; J^ = J^z ; J^x iJ^y (4.100)
4.4. ANGULAR MOMENTUM EIGENVALUE EQUATION 109
which can be written as

h i h i h i
J^z ; J^ = J^z ; J^x i J^z ; J^y = i~J^y i i~J^x (4.101)
h i
) J^z ; J^ = i~J^y ~J^x = ~ J^x iJ^y (4.102)
that leads to the commutator
h i
J^z ; J^ = ~J^ : (4.103)
On the other hand the commutator between J^2 and J^

h i h i h i
J^2 ; J^ = J^2 ; J^x iJ^y = J^x2 + J^y2 + J^z2 ; J^x iJ^y
h i h i h i h i
= J^y2 ; J^x + J^z2 ; J^x i J^x2 ; J^y i J^z2 ; iJ^y (4.104)
Applying the relation

h i h i h i
^ B
A; ^ C^ = B
^ A;^ C^ + A;
^ B
^ C^ (4.105)
we may write
h i h i h i
J^x ; J^y2 = J^y J^x ; J^y + J^x ; J^y J^y = i~ J^y J^z + J^z J^y ; (4.106)
h i h i h i i h
J^x ; J^z2 = J^z J^x ; J^z + J^x ; J^z J^z = i~ J^z J^y + J^y J^z =
J^x ; J^y2 ;
h i h i h i (4.107)
^ ^2 ^ ^ ^ ^ ^ ^ ^ ^
Jy ; Jx = Jx Jy ; Jx + Jy ; Jx Jx = i~ Jx Jz + Jz Jx ; ^ ^ (4.108)
h i h i h i h i
J^y ; J^z2 = J^z J^y ; J^z + J^y ; J^z J^z = i~ J^z J^x + J^x J^z = J^y ; J^x2 (4.109)
so that h i
J^2 ; J^ = 0: (4.110)
How does J^+ J^ raise (lower) the eigenstates?: From Eq. (17.47) we
have
J^z J^ = J^ J^z ~J^ : (4.111)
so that
J^z J^ j ; mi = J^ J^z ~J^ j ; mi = J^ J^z j ; mi ~J^ j ; mi
= ~mJ^ j ; mi ~J^ j ; mi ) J^z J^ j ; mi = ~ (m 1) J^ j ; mi

(4.112)
The result in Eq. (??)shows that the state J^ j ; mi is an eigenstate of J^z with
an eigenvalue ~ (m 1) : Therefore, we must have
J^ j ; mi = C ( ; m) j ; m 1i : (4.113)
so that the eigenvalue equation for J^z is satis…ed

J^z C ( ; m) j ; m 1i = ~ (m 1) C ( ; m) j ; m 1i
) J^z j ; m 1i = ~ (m 1) j ; m 1i (4.114)
From Eq. (4.113) we note that
J^+ j ; mi = C+ ( ; m) j ; m + 1i (4.115)
where the state has raised by one and
J^ j ; mi = C ( ; m) j ; m 1i (4.116)
the state is lowered by one. This is the reason why these operators are called
raising and lowering operators.
The eigenvalues: we now proceed to determine the eigenvalues and m for
J^2 and J^z , respectively. To this end, we begin with the maximum value for m:
Suppose the measured value for the total angular momentum for the system is
j; = j: It is physically obvious that the measured value of z-component of the
angular momentum can not exceed this value. Then one can make the argument
that the maximum eigenvalue for J^z must be
mmax = j: (4.117)
hen since this is the maximum value the state of the system can not be raised
any further. This means, we must have
J^+ j ; ji = 0 ) J^ J^+ j ; ji = 0: (4.118)
Using
h i
J^ J^+ = J^x iJ^y J^x + iJ^y = J^x2 + J^y2 + i J^x ; J^y
= J^x2 + J^y2 ~J^z ) J^ J^+ = J^2 J^z2 ~J^z (4.119)
we may write equation Eq. (4.118) as
J^2 J^z2 ~J^z j ; ji = 0 ) ~ j2 j j ; ji = 0: (4.120)
which leads to
~ j2 j =0) = j (j + 1) (4.121)
Let’s say for a given system the measured minimum value for J^z be mmin = j 0 ,
then since one can not lower the state of this system any further down,
J^ j ; j 0 i = 0 ) J^+ J^ j ; j 0 i = 0: (4.122)
Using
h i
J^ J^+ = J^x iJ^y J^x + iJ^y = J^x2 + J^y2 i J^x ; J^y
= J^x2 + J^y2 + ~J^z ) J^+ J^ = J^2 J^z2 + ~J^z (4.123)
we may write equation Eq. (??) as
J^2 J^z2 + ~J^z j ; j 0 i = 0 ) ~ j 02 j 0 j ; ji = 0

)~ j 02 j0 = 0 ) = j 0 (j 0 + 1) (4.124)
Since the operators J^ and J^z commute the measurement of J^z does not a¤ect
the measured value for J:^ Therefore what we must have the same value for
measured total angular momentum, J^ . That means
= j (j + 1) = j 0 (j 0 + 1) ) j 02 j 0 j (j + 1) = 0
p
0 1 1 4j (j + 1)
)j = (4.125)
2
There follows that
j 0 = j + 1 or j 0 = j (4.126)
As we recall mmax = j is the maximum value that can be measured for J^z and
the system can not have any higher value. Therefore, physically the acceptable
minimum eigenvalue for J^z must be
mmin = j 0 = j (4.127)
Though we do not know, yet, the values for j, we do know the lower and upper
limits for the eigenvalues to J^z in terms of j
j m j: (4.128)
and also from Eqs. (4.117) and (4.127) one can establish the relation
mmax mmin = 2j: (4.129)
Since J^ lowers the state by one, starting from the state where m takes the
maximum value, mmax = j; (See Fig.4.5) where we have
J^ jj; ji = jj; j 1i ; J^2 jj; ji = jj; j 2i ; J^3 jj; ji = jj; j 3i ::::

^2j 2
J jj; ji = jj; j + 2i ; J^2j 1 jj; ji = jj; j + 1i
^2j
J jj; ji = jj; ji (4.130)
on can easily show that

1 3 5
2j 0 ) j = 0; ; 1; ; 2; ; :::
2 2 2
We recall that for the raising and lowering operators,
J^+ jj; mi = C+ (j; m) jj; m + 1i (4.131)
and
J^ jj; mi = C (j; m) jj; m 1i : (4.132)
Figure 4.5: Lowering of the state by successively operating J^ on the state jj; ji
the lowest state jj; ji :
Next we want to determine C+ (j; m) and C+ (j; m) : To this end we note that
y
hj; mj J^+ = hj; mj J^ = hj; m + 1j C+ (j; m) (4.133)
and
hj; mj J^y = hj; mj J^+ = hj; m 1j C (j; m) (4.134)
where we used the relation
y
J^+ = J^ ; J^+ = J^y : (4.135)
Using Eqs. (4.133) and (4.134), we have
hj; mj J^ J^+ jj; mi = hj; m + 1j C+ (j; m) C+ (j; m) jj; m + 1i

2
= jC+ (j; m)j hj; m + 1j j; m + 1i
2
) jC+ (j; m)j = hj; mj J^ J^+ jj; mi (4.136)
We recall that since = j (j + 1), the eigenvalue equations
J^2 j ; mi = ~2 j ; mi ; J^z j ; mi = ~m j ; mi ; (4.137)
should be written as
J^2 jj; mi = ~2 j (j + 1) jj; mi ; J^z jj; mi = ~m jj; mi : (4.138)
The one write
J^ J^+ = J^2 J^z2 + ~J^z ) J^ J^+ jj; mi = J^2 J^z2 + ~J^z jj; mi
) J^ J^+ jj; mi = ~2 j (j + 1) m2 + m jj; mi (4.139)
one can write

2
jC+ (j; m)j = hj; mj J^ J^+ jj; mi = ~2 [j (j + 1) m (m + 1)]
p
) C+ (j; m) = ~ j (j + 1) m (m + 1)
Following a similar procedure one can show that

p
C (j; m) = ~ j (j + 1) m (m 1)
So that the equation for the raising and lowering operators equation becomes
p
J^+ jj; mi = ~ j (j + 1) m (m + 1) jj; m + 1i (4.140)
and p
J^ jj; mi = ~ j (j + 1) m (m 1) jj; m 1i : (4.141)
Example 4.3 For j = 1=2

(a) Determine all the basis states (i.e. the angular momentum eigenstates) and
name a particle that can have these states.
(b) Determine the matrix representation of J^z ; J^+ ; and J^ using the corre-
sponding basis states.
(c) Use the result J^+ ; and J^ in part (b) and …nd the matrix representation
for J^x ; and J^y
(d) Solve the eigen value equation for J^z ; J^y and J^x :
Solution:
(a) Noting that

j = 1=2 ) m = 1=2; 1=2
The basis states can be written as
1 1 1 1 1
for j = ) ; and ; ;
2 2 2 2 2
(b) For j = 1=2
1
2;
1
2 J^z 12 ; 12 1 1 ^
2 ; 2 Jz
1
2;
1
2
Jz = ; (4.142)
1
2;
1
2 J^z 12 ; 12 1
2;
1 ^
2 Jz
1
2;
1
2
1
2;
1
J^ 12 ; 21 1 1 ^
2; 2 J
1
2;
1
J^ = 2 2 (4.143)
1
2;
1
2 J^ 12 ; 12 1
2;
1 ^
2 J
1
2;
1
2
Taking into consideration one can not raise the state more than the max-
imum value or lower than the minimum value, we can write for j = 1=2
0 1
2;
1
J^+ 12 ; 1 1
2;
1
J^ 1 1
2; 2 0
J^+ = 2 2 ; J^ = 2
0 1
2;
1
2 J^+ 1 ; 2
1
2
1
2;
1
2 J^ 1 1
2; 2 0
Applying the relations

p
J^z jj; mi = ~m jj; mi ; J^ jj; mi = ~ j (j + 1) m (m 1) jj; m 1i
(4.144)
we have
1 1 ~ 1 1
J^z ; = ; ;
2 2 2 2 2
1 1 1 1 1 1 1 1
J^+ ; = ~ ; ; J^ ; =~ ;
2 2 2 2 2 2 2 2
so that
~ 1 0 0 1 0 0
Jz = ; J^+ = ~ ; J^ = ~
2 0 1 0 0 1 0
(c) Recalling that the raising and lowering operators can be expressed as
J^+ = J^x + iJ^y ; J^ = J^x iJ^y (4.145)
one can write

1 ^ 1 ^
J^x = J+ + J^ ; J^y = J+ J^ : (4.146)
2 2i
The matrix representation,
1 ~ 0 1 ~ 0 0 ~ 0 1
Jx = (J+ + J ) = + = (4.147)
;
2 2 0 0 2 1 0 2 1 0
1 ~ 0 1 ~ 0 0 ~ 0 i
Jy = (J+ J ) = = (4.148)
:
2i 2i 0 0 2i 1 0 2 i 0
The matrices Jx , Jy ; and Jz can be put in the form
~ ~ ~
Jx = x ; Jy = y ; Jz = z (4.149)
2 2 2
where the matrices x; y; and z
0 1 0 i 1 0
x = ; y = ; z = ; (4.150)
1 0 i 0 0 1
are known as the Pauli spin matrices.

(d) The eigenvalue problem for J^x ; J^y ; and J^z are given by
J^z jY i = z jY i ; J^y jY i = y jY i ; J^x jXi = x jXi ; (4.151)
where x ; jXi ; y ; jY i ; and z ; jZi are the eigenvalues and eigen vectors
for J^x ; J^y ;and J^z ; respectively. Using matrices one can write
1
2;
1
2 J^z 12 ; 12 1
2;
1
2 J^z 12 ; 1
2 c1
1
2;
1
2 J^z 12 ; 12 1
2;
1
2 J^z 12 ; 1
2
c2
c1
= z ;
c2
1
2;
1
2 J^y 12 ; 12 1
2;
1
2 J^y 12 ; 1
2 b1
1
2;
1
2 J^y 21 ; 12 1
2;
1
2 J^y 12 ; 1
2
b2
b1
= y
b2
1
2;
1
2 J^x 12 ; 12 1
2;
1
2 J^x 12 ; 1
2 a1
1
2;
1
2 J^x 12 ; 12 1
2;
1
2 J^x 12 ; 1
2
a2
a1
= x ; (4.152)
a2
where
1 1 1 1
c1 2; 2 Zi b1 2; 2 Yi
= 1 1 ; = 1 1 ;
c2 2; 2 Zi b2 2; 2 Yi
1 1
a1 2; 2 Xi
= 1 1 : (4.153)
a2 2; 2 Xi
We have already determined the matrix representation of the operators in

part (c). Using these results,
~ 1 0 c1 c1
= z ;
2 0 1 c2 c2
~ 0 i b1 b1
= y ;
2 i 0 b2 b2
~ 0 1 a1 a1
= x : (4.154)
2 1 0 a2 a2
and the identity matrix, one can write

~
2 z 0 c1
~ = 0;
0 2 + z c2
i~
y 2 b1
i~ = 0;
2 y b2
~
x 2 c1
~ = 0: (4.155)
2 x c2
Applying what we learn in Theoretical physics I, we have

~
2 z 0
det ~ = 0;
0 2 + z
i~
y 2
det i~ = 0;
2 y
~
x 2
det ~ = 0; (4.156)
2 x
so that
2 2
~ ~ 2 ~ 2 ~
z + z = 0; y = 0; x =0
2 2 2 2
which leads to
~ ~ ~ ~ ~ ~
z1 = ; z2 = ; y1 = ; y2 = ; x1 = ; y2 = :
2 2 2 2 2 2
The corresponding eigen vectors can be determined as follows:
~
For Jz ; using z1 = 2
~ ~
2 2 0 c1
~ ~ = 0 ) c2 = 0;
0 2 + 2
c2
1
) jZ1 i = c1 ; (4.157)
0
~
and z2 = 2
~ ~
2 + 2 0 c1
~ ~ = 0 ) c2 = 0;
0 2 2
c2
0
) jZ2 i = c2 ; (4.158)
1
upon normalizing these eigen vectors, one …nds
~ ~
2 2 0 c1
~ ~ = 0 ) c2 = 0;
0 2 + 2
c2
1
) jZ1 i = c1 ; (4.159)
0
~
and z2 = 2
1 0
jZ1 i = ; jZ2 i = ; (4.160)
0 1
Recalling that
1 1
c1 2; 2 Zi
= 1 1 (4.161)
c2 2; 2 Zi
one can then write
1 1 1 1 1 1
jZ1 i = ; = ; jZ2 i = ; (4.162)
2 2 2 2 2 2
1
Note that j Zi = 2 is what we introduced to in the previous chapter
for a spin-half particle.
~
For Jy ; using y1 = 2
~ i~
2 2 b1
i~ ~ = 0;
2 2
b2
~ i~ 1
) b1 b2 = 0; ) b2 = ib1 ) jY1 i = b1 ; (4.163)
2 2 i
~
and y2 = 2
~ i~
2 2 b1
i~ ~ = 0;
2 2
b2
~ i~ 1
) b1 b2 = 0; ) b2 = ib1 ) jY2 i = b1 ; (4.164)
2 2 i
1 1 1 1
jY1 i = p ; jY2 i = p ; (4.165)
2 i 2 i
Recalling that
1 1
b1 2; 2 Yi
= 1 1 (4.166)
b2 2; 2 Yi
one can then write
1 1 1 1 1
jY1 i = p ; +i ;
2 2 2 2 2
1 1 1 1
= p +i ;
2 2 2 2
1 1 1 1 1
jY2 i = p ; i ;
2 2 2 2 2
1 1 1 1
= p i ; (4.167)
2 2 2 2
Note that
1 1 1 1 1 1
j+Y i = p +i ;j Y i = p i
2 2 2 2 2 2
are what we introduced for spin-half particle in the in the z-basis. Finally
for Jx ; using x1 = ~2
~ ~
2 2 a1
~ ~ = 0;
2 2
a2
~ ~ 1
) b1 + b2 = 0; ) b2 = b1 ) jX1 i = b1 ; (4.168)
2 2 1
~
and x2 = 2
~ ~
2 2 b1
~ ~ = 0;
2 2
b2
~ ~ 1
) b1 + b2 = 0; ) b2 = b1 ) jX2 i = b1 ; (4.169)
2 2 1
1 1 1 1
jX1 i = p ; jX2 i = p ; (4.170)
2 1 2 1
Recalling that
1 1
b1 2; 2 Xi
= 1 1 (4.171)
b2 2; 2 Xi
one can then write

1 1 1 1 1
jX1 i = p ; + ;
2 2 2 2 2
1 1 1 1
= p + ;
2 2 2 2
1 1 1 1 1
jX2 i = p ; ;
2 2 2 2 2
1 1 1 1
= p ; (4.172)
2 2 2 2
Note that
1 1 1 1 1 1
j+Xi = p + ; j Xi = p
2 2 2 2 2 2
are also what we introduced for spin-half particle in the in the z-basis.
Example 4.4 For j = 1
(a) Determine all the basis states (i.e. the angular momentum eigenstates) and
name a particle that can have these states.
for J^x ; and J^y
(d) Solve the eigen value equation for J^z :

Solution:
(a) Noting that
j=1)m= 1; 0; 1
j = 1 ) j1; 1i ; j1; 0i and j1; 1i :
(b) The matrix representations for the operators are given by

0 1
h1; 1j J^z j1; 1i h1; 1j J^z j1; 0i h1; 1j J^z j1; 1i
Jz = @ h1; 0j J^z j1; 1i h1; 0j J^z j1; 0i h1; 0j J^z j1; 1i A (4.173)
h1; 1j Jz j1; 1i h1; 1j J^z j1; 0i
^ h1; 1j J^z j1; 1i
and
0 1
h1; 1j J^ j1; 1i h1; 1j J^ j1; 0i h1; 1j J^ j1; 1i
J^ = @ h1; 0j J^ j1; 1i h1; 0j J^ j1; 0i h1; 0j J^ j1; 1i A (4.174)
h1; 1j J^ j1; 1i h1; 1j J^ j1; 0i h1; 1j J^ j1; 1i
Taking into consideration one can not raise the state more than the max-
imum value or lower than the minimum value, we can write
0 1
0 h1; 1j J^+ j1; 0i h1; 1j J^+ j1; 1i
J^+ = @ 0 h1; 0j J^+ j1; 0i h1; 0j J^+ j1; 1i A (4.175)
0 h1; 1j J^+ j1; 0i h1; 1j J^+ j1; 1i
0 1
h1; 1j J^ j1; 1i h1; 1j J^ j1; 0i 0
J^ = @ h1; 0j J^ j1; 1i h1; 0j J^ j1; 0i 0 A (4.176)
h1; 1j J j1; 1i h1; 1j J^ j1; 0i 0
^
Applying the relations

p
J^z jj; mi = ~m jj; mi ; J^ jj; mi = ~ j (j + 1) m (m 1) jj; m 1i
(4.177)
we have
J^z j1; 1i = ~ j1; 1i ; J^z j1; 0i = 0;
p p
J^+ j1; 0i = ~ 2 j1; 1i ; J^+ j1; 1i = ~ 2 j1; 1i ;
p p
J^ j1; 1i = ~ 2 j1; 0i ; J^ j1; 0i = ~ 2 j1; 1i ;
so that for
0 1 0 1 0 1
1 0 0 p 0 1 0 p 0 0 0
Jz = ~ @ 0 0 0 A ; J^+ = ~ 2 @ 0 0 1 A ; J^ = ~ 2 @ 1 0 0 A
0 0 1 0 0 0 0 1 0
(4.178)
(c) We recall that the raising and lowering operators can be expressed as
J^+ = J^x + iJ^y ; J^ = J^x iJ^y (4.179)
so that
1 ^ 1 ^
J^x = J+ + J^ ; J^y = J+ J^ : (4.180)
2 2i
The matrix representation
0 1 0 1
0 1 0 0 0 0
1 ~ ~
Jx = (J+ + J ) = p @ 0 0 1 A+ p @ 1 0 0 A
2 2 2
0 0 0 0 1 0
0 1
0 1 0
~
) Jx = p @ 1 0 1 A; (4.181)
2 0 1 0
0 1 0 1
0 1 0 0 0 0
1 i~ @ i~
Jy = J )= p
(J+ 0 0 1 A+ p @ 1 0 0 A
2i 2 2
0 0 0 0 1 0
0 1
0 i 0
~ @
) Jy = p i 0 i A; (4.182)
2 0 i 0
We note that the three Jx , Jy ; and Jz

0 1 0 1
1 0 0 0 i 0
~
Jz = ~ @ 0 0 0 A ; Jy = p @ i 0 i A;
0 0 1 2 0 i 0
0 1
0 1 0
~
Jx = p @ 1 0 1 A
2 0 1 0
can be put in the form
Jx = ~ x ; Jy =~ y ; Jz =~ z (4.183)
where the matrices x; y; and z
0 1 0 1
0 pi 0
1 0 0 2
@ A B pi 0 pi C
z = 0 0 0 ; y=@ 2 2 A ; (4.184)
0 0 1 0 pi 0
2
0 1
1
0 p
2
0
B p1 0 p1 C
x = @ 2 2 A
: (4.185)
1
0 p
2
0
What shall we call these matrices? Pauli spin-1 matrices???

(d) The eigenvalue problem for J^x is given by
J^x jXi = x jXi : (4.186)
Using matrices one can write

0 ^ j1; 1i 10 1
h1; 1j Jx h1; 1j J^x j1; 0i h1; 1j J^x j1; 1i a1
@ h1; 0j J^x j1; 1i h1; 0j J^x j1; 0i h1; 0j J^x j1; 1i A @ a2 A
h1; 1j Jx j1; 1i h1; 1j J^x j1; 0i
^ h1; 1j J^x j1; 1i a3
0 1
a1
= x
@ a2 A ; (4.187)
a3
where 0 1 0 1
a1 h1; 1j Xi
@ a2 A = @ h1; 0j Xi A : (4.188)
a3 h1; 1j Xi
We have already determined the matrix representation of the operator in
part (c). Using these result, we may write
0 10 1 0 1
0 1 0 a1 a1
~ @
p 1 0 1 A @ a2 A = x @ a2 A ;
2 0 1 0 a a
3 3
Using the identity matrix, these equations can be put in the form
0 ~
10 1
x p
2
0 a1
B p~ C@
@ 2 x p~
2 A
a2 A = 0: (4.189)
~ a
0 p x 2
3
There follows that

0 ~
1
x p
2
0
B ~ ~ C
det @ p
2 x p
2 A=0
~
0 p
2 x
~
p ~ ~
x 2 ~ p p
) x ~ p 2 2 =0
p
2 x 2 0 x
!
2 2
2 ~ ~
) x x p + xp =0
2 2
" #
2 2
2 ~ ~
) x x p p =0
2 2
2
) x x ~2 = 0 ) 1x = ~; 2x = 0; 3x = ~ (4.190)
Then corresponding eigen vectors, for 1x = ~
0 10 1
~ p~2 0 a1
B p~ ~ p~2 C
@ 2 A @ a2 A = 0: (4.191)
~ a3
0 p
2
~
Homework For j = 3=2

(a) Determine all the basis states (i.e. the angular momentum eigenstates).
for J^x ; and J^y
(d) Solve the eigen value equation for J^y :
Solution:
(a) Noting that
j = 3=2 ) m = 3=2 1=2; 1=2; 3=2 (4.192)
3 3 3 3 1 3 1 3 3
j= ) ; ; ; ; ; and ; :
2 2 2 2 2 2 2 2 2
(b)
Chapter 5
Time evolution of a
quantum system
A system that is subjected to interaction, its state undergoes changes with time.
This change of state can result in changes in the measurement of the physical
observables with time. In this section we will learn how time dependent state
vectors and the operators representing the physical observables evolve in time.
We will be introduced to the governing equation of motion and how we solve
these equation of motion in quantum mechanics.
5.1 The evolution operators and the Schrödinger

equation
Consider a quantum system described by a state vector, j (0)i ; at the initial
time t = 0: Just like the rotation operators R ^ ('^ ^ ('^
x) ; R ^ ('^
y ) ; and R z ) ; we
introduced to that changes the state vector in space, there must be an operator,
U^ (t) ; the evolution operator that changes this state vector in time into a new
state j (t)i ;
^ (t) j (0)i :
j (t)i = U (5.1)
Using the bra vector
^ y (t) ;
h (t)j = h (t)j U (5.2)
we note that
h (t)j ^ y (t) U
(t)i = h (0)j U ^ (t) j (0)i = 1; (5.3)
Since the state vector remains normalized all the time
h (0)j (0)i = 1; (5.4)
there follows that
^ y (t) U
U ^ (t) = 1 ) U
^ y (t) = U
^ 1
(t) : (5.5)
123
124 CHAPTER 5. TIME EVOLUTION OF A QUANTUM SYSTEM
This shows that the evolution operator is unitary.

^ for example for a rotation about the
We recall for the rotation operator R,
z axis, we had
R^ ('k) = 1 i J^z '; (5.6)
~
in terms of the rotation generator operator J^z : This operator rotates the particle
spin in space and therefore changes the state vector. Here the evolution operator
translates the particle in time and therefore changes the state vector. Similarly,
we may express the evolution operator as
^
iH
^ (t) = 1
U t; (5.7)
~
where H ^ is the quantum Hamiltonian (total energy operator). For a state
translation by an in…nitessimal time interval t, like an in…nitesimal rotation
'; one can write the evolution operator as
^
iH
^ ( t) = 1
U t: (5.8)
~
Suppose we translate the state …rst by a time t
^ ( t) j (0)i ;
j ( t)i = U (5.9)
followed by a time t; so that the state at t + t becomes
j (t + ^ (t) j ( t)i = U
t)i = U ^ (t) U
^ ( t) j (0)i ; (5.10)
Noting that using the evolution operator at t + t; one can also write that
j (t + ^ (t +
t)i = U t) j (0)i ; (5.11)
one can establish the relation

!
^
iH ^ (t) H
iU ^
^ (t +
U ^ (t) U
t) = U ^ ( t) = U
^ (t) 1 t ^ (t)
=U t: (5.12)
~ ~
There follows that

^ (t +
U t) U^ (t) ^ (t) H
iU ^
= : (5.13)
t ~
so that for an in…nitessimal t, we …nd
^ (t)
dU ^ (t +
U t) ^ (t)
U ^ (t) H
iU ^
= lim = : (5.14)
dt t!0 t ~
There follows that
dU^ (t) ^
iH ^
iH
= ^ (t) = e
dt ) U ~ t
: (5.15)
^
U (t) ~
5.2. ENERGY EIGENVALUE EQUATION AND THE STATE VECTOR125
The state vector at time t, can then be expressed as

^
iH
^ (t) j (0)i = e
j (t)i = U ~ t
j (0)i : (5.16)
so that
d d ^
iH ^
iH ^
iH ^
iH
t t
j (t)i = e ~ j (0)i = e ~ j (0)i = j (t)i : (5.17)
dt dt ~ ~
This equation which can be put in the form
d ^ j (t)i
i~ j (t)i = H (5.18)
dt
is known as the Schrödinger equation. The Schrödinger equation is the governing
equation of motion in quantum mechanics just like Newton’s equation of motion
d2~r (t)
F~ (t) = m (5.19)
dt2
where m is the mass and ~r (t) is the position of the object, F~ (t) is the total
force acting on the object at a given time, t.
5.2 Energy eigenvalue equation and the state

vector
The state vector has a special relationship with the energy eigenstate. We have
stated that the quantum Hamiltonian H; ^ is just the total energy operator. One
can write the eigenvalue equation for this operator as
^ jEn i = En jEn i
H (5.20)
where jEn i and En are the eigenstate and eigenvalue for the energy operator.
Suppose there exists N eigenstates fjE1 i ; jE2 i ; jE3 i ::: jEN ig with the corre-
sponding eigenvalues fE1 ; E2 ; E3 :::EN g : Using the completeness relation for
these eigenstates
N
X
jEn i hEn j = I (5.21)
n=1
one can express the state vector as

N
X N
X
^
iH ^
iH ^
iH
t t t
j (t)i = e ~ j (0)i = e ~ jEn i hEn j (0)i = e ~ jEn i hEn j (0)i :
n=1 n=1
(5.22)
so that noting that
^
iH iEn
t t
e ~ jEn i = e ~ jEn i
one …nds
N
X N
X
iEn iEn
t t
j (t)i = e ~ jEn i hEn j (0)i = e ~ cn jEn i : (5.23)
n=1 n=1
where
cn = hEn j (0)i (5.24)
is the probability amplitude for the particle is in the state jEn i at the initial
time t = 0. We can also rewrite the state vector in a di¤erent form
N
X N
X
iEn
t
j (t)i = e ~ jEn i hEn j (0)i = cn (t) jEn i ; (5.25)
n=1 n=1
where
iEn
t
cn (t) = e ~ hEn j (0)i (5.26)
is the probability amplitude that the particle be in the state at the a given time
t:
5.3 The Heisnberg and the interaction picture

In quantum description of a given system, what we basically do involves the
following three steps
(a) Determine the quantum Hamiltonian, H, ^ (generally from the classical Hamil-
tonian). For example, for a one dimensional classical Harmonic oscillator
oscillating in the x-direction, the total energy (the Hamiltonian) which is
the sum of the kinetic and elastic potential energy is given by
1 1
H= mv 2 + kx2 (5.27)
2 x 2
where m is the mass, vx is the velocity in the x-direction, and k is the
spring constant. Usually in classical mechanics kinetic energy is expressed
in terms of momentum, px = mvx ; so that one can write the Hamiltonian
in the form
2
p2x 1 1 dx 1 x_ 2 1
H= + kx2 = + kx2 = + kx2 : (5.28)
2m 2 2m dt 2 2m 2
In quantum mechanics we replace the observable (the momentum and

position in this case) by operators and the quantum Hamiltonian is written
as
2
^ = p^x + 1 k^
H x2 : (5.29)
2m 2
5.3. THE HEISNBERG AND THE INTERACTION PICTURE 127
(b) For the quantum Hamiltonian determined, we solve the Schrödinger equa-
tion
d ^ j (t)i :
i~ j (t)i = H (5.30)
dt
(c) We can then …nd the expectation values for any physical observable, A^ (t) ;
we are interested in
D E
A^ (t) = h (t)j A^ j (t)i : (5.31)
This approach is referred as Schrödinger picture in quantum optics. But I

tell you that, in real quantum systems, sometimes this general approach does not
work. For example, solving Schrödinger equation can be extremely di¢ cult. In
such cases quantum physicist prefer to use alternative approaches. The approach
are referred as, in quantum optics, the Heisenberg and the interaction picture. I
will introduce you to these approaches which you may need when you deal with
real quantum mechanical system, especially in quantumD optics. E
The Heisenberg picture: For the expectation value, A^ (t) ; one can write
D E
A^ (t) = h (t)j A^ j (t)i = h (0)j U^ y (t) AÛ
^ (t) j (0)i = h (0)j A^ j (0)i :
(5.32)
where
A^ (t) = U
^ y (t) AÛ
^ (t) : (5.33)
Di¤erentiating this equation with respect to time
! !
d ^ d h ^y ^ ^
i dU^ y (t) ^ (t)
dU
A (t) = U (t) AU (t) = AÛ
^ (t) + U
^ y (t) A^
dt dt dt dt
!
@ ^
A
^ (t)
+U y
U^ y (t) : (5.34)
@t
Note that the third terms exists when the operator is explicitly depends on time.
That means for example, for the momentum operator, p^x ; instead of
d
p^x = i~
dx
if it depends explicitly on time
d @ A^
p^x = i~ + xt ) = x
dx @t
then the third term won’t be zero. Using
^
iH dU^ (t) ^ iH^
iH ^
iH
^ (t)
U = e ~ t
) = e ~t= U^ (t) (5.35)
dt ~ ~
" #y
^ y (t)
dU iH^
) = U^ (t) = i U ^ y (t) H^y = i U ^ y (t) H
^ (5.36)
dt ~ ~ ~
one can write

!
d ^ i ^y ^
iH
A (t) = ^ AÛ
U (t) H ^ (t) ^ y (t) A^ (0)
U ^
U (t) : (5.37)
dt ~ ~
Noting that
h i h ^
iH
i
^ U
H; ^ (t) = H;
^ e ~ t Û
=0)H ^ (t) = U
^ (t) H
^ )H
Û^ y (t) = U
^ y (t) H
^
(5.38)
we may write
!
d ^ i n ^ ^y o @ A^
A (t) = H U (t) AÛ
^ (t) U (t) AÛ
^y ^ (t) H
^ + U (t) ^y ^ (t)
U
dt ~ @t
!
i n^ ^ o @ A^
= H A (t) A^ (t) H
^ +U^ y (t) ^ (t) :
U (5.39)
~ @t
Substituting
^ ^
A^ (t) = U
^ y (t) AÛ ^ y (t) @ A U
^ (t) ; @ A (t) = U ^ (t) : (5.40)
@t @t
one can write
d ^ i h ^ ^ i @ A^ (t)
A (t) = H; A (t) + : (5.41)
dt ~ @t
This equation is the Heisenberg equation. In most real quantum mechanical
systems operators do not explicitly depend on time and
@ A^ (t)
=0 (5.42)
@t
and the Heisenberg equation becomes
d ^ i h^ ^ i
A (t) = H; A (t) : (5.43)
dt ~
Therefore, in the Heisenberg picture the time dependence is carried by the
operators. For a particle initially, t = 0, in the state j (0)i ; the expectation
value for the physical observable represented by the operator, A^ (t) ; at a later
time, t, can then be determined using
D E
A^ (t) = h (0)j A^ (t) j (0)i : (5.44)
where A^ (t) is determined by solving the Heisenberg equation.

The interaction picture: We may chose the interaction picture when often
face situations where we already know the solutions of the problem in the ab-
sence of interaction and the free and interaction part of the Hamiltonian do
commute. Suppose in the absence of interaction the Hamiltonian describing the
^ F and the part that describe the interaction

system (the free Hamiltonian) is H
^
be HI so that the total Hamiltonian becomes
^ =H
H ^F + H
Î : (5.45)
When these two parts of the Hamiltonian commutes

h i
H^F ; H
^ I = 0; (5.46)
one can express the evolution operator

^
^ (t) = e
U
iH
~ t
=e
i
~ (H^ F +H^ I )t = e i ^
~ HF t e
i ^
~ HI t =e
i ^
~ HI t e
i ^
~ HF t : (5.47)
If the system, initially, is described by the state vector j (0)i, then at a later
time t, one can write
^
iH i ^ i ^ i ^
t ~ HF t ~ HI t ~ HF t
j (t)i = e ~ j (0)i = e e j (0)i = e j I (t)i ; (5.48)
where we introduced the interaction state vector

i ^
j (t)i = e ~ HI t j (0)i : (5.49)
I
Now using the Schrödinger equation

d ^ j (t)i ;
i~ j (t)i = H (5.50)
dt
we may write
d h i ^
i h
^F + H
ih
Î e i ^
i
i~ e ~ HF t j (t)i = H ~ HF t j (t)i
I I
dt
i ^ d i ^ i ^
) i~e ~ HF t j (t)i + i~ HF e ~ HF t j (t)i
dt I ~ I
h ih i ^
i
= H ^F + H
Î e ~ HF t j
I (t)i
i ^ d Î e i ^
) i~e ~ HF t j (t)i = H ~ HF t j (t)i :
I I
dt
Applying the commutation h i
H^F ; H
^ I = 0: (5.51)
one …nds
i ^ d i ^
^ I j I (t)i :
e ~ HF t i~ j I (t)i = e ~ HF t H
dt
d ^ I j I (t)i ;
) i~ j I (t)i = H (5.52)
dt
which involves only the interaction part of the Hamiltonian.
Example 1 Precession of spin-1/2 particle in a magnetic …eld: Consider an

electron (charge, q = e and mass, me ) with magnetic dipole moment
m:
~ Somebody turned on a uniform magnetic …eld B0 directed along the
positive z-axis.
(a) Determine the classical and quantum Hamiltonians.
(b) Solve the eigenvalue equation for the quantum Hamiltonian.
(c) Determine the state of the electron at a later time t if the initially state of
the electron, j (0)i = j+Zi and j (0)i = j+Xi :
(d) Using the state vector determined in (d) …nd the probabilities P+z (t) and
P z (t) ; P+x (t) and P x (t) for both initial states.
D E D E D E
(e) Find the expectation values for S^z ; S^x ; and S^y when the particle
is initially in state j (0)i = j+Xi :
(f ) Verify the results you determined in (e) using the Heisenberg equation
d ^ i h^ ^ i
A (t) = H; A (t) : (5.53)
dt ~
Solution:
(a) In chapter one we were introduced to the magnetic energy of a magnetic
dipole in a uniform magnetic …eld. This energy (the classical Hamiltonian)
is given by
H= m ~ B ~ ) H = ge S ~ B~ (5.54)
2me c
where used the spin magnetic moment
ge ~
m
~ = S (5.55)
2me c
for an electron. For a uniform magnetic …eld directed along the z-axis
~ = B0 z^;
B (5.56)
we have
~ B
S ~ = B0 Sz (5.57)
so that
geB0
H= Sz (5.58)
2me c
The quantum Hamiltonian is obtained by replacing the variables repre-
senting the physical observables that the energy depends on by operators.
In this case the variable that determines the energy is the z-componet of
the spin. Thus the quantum Hamiltonian becomes
^ = geB0 S^z = ! 0 S^z ;

H (5.59)
2me c
where
geB0
!0 = : (5.60)
2me c
(b) Since h i h i
^ S^z = ! 0 S^z ; S^z = 0;
H; (5.61)
the two operators must have the same eigenstates. Then using the eigen-
value equation for S^z ; one …nds
~ ~! 0
S^z j Zi = ^ j Zi =
j Zi ) H j Zi : (5.62)
2 2
(c) Generally, if the particle is initial in a state j (0)i, the state vector at a
later time, t, is determined by the evolution operator which depends on
the quantum Hamiltonian
^
iH i ^
t ~ ! 0 Sz t
j (t)i = e ~ j (0)i = e j (0)i : (5.63)
For an initial state

j (0)i = j+Zi ; (5.64)
we …nd !0
i ^
j (t)i = e ~ ! 0 Sz t j+Zi = e i 2 t
j+Zi : (5.65)
On the other hand for an initial state
1
j (0)i = j+Xi = p [j+Zi + j Zi] ; (5.66)
2
the state vector becomes
i ^ 1 h i ^ i ^
i
j (t)i = e ~ ! 0 Sz t
j+Xi = p e ~ !0 Sz t j+Zi + e ~ ! 0 Sz t j Zi
2
1 h i !0 t !0
i
) j (t)i = p e 2 j+Zi + ei 2 t j Zi : (5.67)
2
(d) For the initial state

j (0)i = j+Zi ; (5.68)
the probabilities at a later time, t, are
2
P+z (t) = jh+Z j (t)ij = h (t) j+Zi h+Z j (t)i
!0 !0
2
= h+Z ei 2 t
j+Zi h+Zj e i 2 t
j+Zi ) P+ (t) = jh+Z j+Zij = 1;
2
P z (t) = jh Z j (t)ij = h (t) j Zi h Z j (t)i
!0 !0
2
= h+Zj ei 2 t
j Zi h Zj e i 2 t
j+Zi ) P (t) = jh Z j+Zij = 0:
(5.69)
For the initial state

1
j (0)i = j+Xi = p [j+Zi + j Zi] ; (5.70)
2
we …nd
1 h !0 !0
i2
2
P+z (t) = jh+Z j (t)ij = p h+Zj e i 2 t j+Zi + ei 2 t j Zi
2
1 !0 !0 1
) P+ (t) = ei 2 t e i 2 t = ; (5.71)
2 2
and
1 h !0 !
i2
2 i 2 t i 20 t
P z (t) = jh Z j (t)ij = p h Zj e j+Zi + e j Zi
2
1 !0 !0 1
) P (t) = ei 2 t e i 2 t = : (5.72)
2 2
Similarly,
2
P+x (t) = jh+X j (t)ij
1 h !0 i 2
1 !0
= p [h+Zj + h Zj] p e i 2 t j+Zi + ei 2 t j Zi
2 2
!0 !0 2 !0 !0 2
i t
e 2 h+Zj +Zi + ei 2 t
h Zj Zi ei 2 t
+e i 2 t
= =
2 2
!0
) P+ (t) = cos2 t ; (5.73)
2
and
2
P (t) = jh X j (t)ij
x
1 h !0 i 2
1 !0
= p [h+Zj h Zj] p e i 2 t j+Zi + ei 2 t j Zi
2 2
!0 !0 2
2
ei
!0
2 t
h+Zj +Zi e i
!0
2 t
h Zj Zi i ei 2 t
e i 2 t
= =
2 2i
!0
)P x (t) = sin2 t : (5.74)
2
Note that in all cases
P+ (t) + P (t) = 1 (5.75)
D E D E
(e) For the expectation values S^z and S^x at a later time, using the results
obtained in part (d), one can easily show that

D E ~ ~
S^z = P+z (t) + P z (t) = 0;
2 2
D E ~ ~
S^x = P+x (t) + P x (t)
2 2
! 0 ~ ! 0 ~
= cos2 t + sin2 t ;
2 2 2 2
D E h !0 !0 i ~ ~
) S^x = cos2 t sin2 t = cos (! 0 t) (5.76)
2 2 2 2
D E
On the other hand for S^y
D E ~ ~
S^y = P+y (t) +P y (t) ;
2 2
we need to determine P+y (t) and P y (t) : We recall that
1
j Y i = p [j+Zi i j Zi] ; (5.77)
2
so that
2
P+y (t) = jh+Y j (t)ij
1 h !0 i 2
1 !0
= p [h+Zj i h Zj] p e i 2 t j+Zi + ei 2 t j Zi
2 2
!0 !0 2 !0 !0 2
i t
e 2 h+Zj +Zi iei 2 t
h Zj Zi e i 2 t
iei 2 t
= = (5.78)
2 2
and
2
P
(t) = jh Y j (t)ij y
1 h !0 i 2
1 !0
= p [h+Zj + i h Zj] p e i 2 t j+Zi + ei 2 t j Zi
2 2
!0 !0 2 !0 !0 2
ei 2 t
h+Zj +Zi + ie i 2 t
h Zj Zi e i 2 t
+ iei 2 t
= = : (5.79)
2 2
Using the relation
i
!0
t !0 !0
e 2 = cos t i sin t ;
2 2
one …nd
2
!0 !0 !0 !0
cos 2 t + sin 2 t i cos 2 t + sin 2 t
P+y (t) =
2
!0 !0
1 + 2 sin 2 t cos 2 t 1 + sin (! 0 t)
= ) P+y (t) = (5.80)
2 2
and
2
!0 !0 !0 !0
cos 2 t sin 2 t + i cos 2 t sin 2 t
P y (t) =
2
!0 !0
1 2 sin 2 t cos 2 t 1 sin (! 0 t)
= )P y (t) = : (5.81)
2 2
Then the expectation value becomes
D E 1 + sin (! 0 t) ~ 1 sin (! 0 t) ~
S^y = + ;
2 2 2 2
D E ~
) S^y = sin (! 0 t) (5.82)
2
(f ) The operators does not explicitly depend on time and we can use the Heisen-
berg equation of the form
d ^ i h^ ^ i
A (t) = H; A (t) : (5.83)
dt ~
Using the quantum Hamiltonian
^ = geB0 S^z = ! 0 S^z ;

H (5.84)
2me c
and the uncertainty relations
h i h i h i
S^x ; S^y = i~S^z ; S^y ; S^z = i~S^x ; S^z ; S^x = i~S^y (5.85)
one can write

d ^ i! 0 h i
Sx = S^z ; S^x = ! 0 S^y ;
dt ~
d ^ i! 0 h i
Sy = S^z ; S^y = ! 0 S^x ;
dt ~
d ^ i! 0 h i
Sz = S^z ; S^z = 0 ) S^z (t) = C (5.86)
dt ~
where C is a constant. Combining the …rst two equations, we …nd
d2 ^ d ^ d2
Sx = !0 Sy ) 2 S^x = ! 20 S^x
dt2 dt dt
d2 ^
) Sx + ! 20 S^x = 0: (5.87)
dt2
The solution of which can be expressed as
S^x (t) = S^1 (0) cos (! 0 t) + S^2 (0) sin (! 0 t) (5.88)

Substituting this into

d ^
Sx = ! 0 S^y ; (5.89)
dt
we …nd
S^y (t) = S^1 (0) sin (! 0 t) S^2 (0) cos (! 0 t) : (5.90)
Then the expectation values becomes
D E
S^z = hCi (5.91)
D E D E
S^y (t) = S^1 (0) sin (! 0 t) S^2 (0) cos (! 0 t)
D E D E D E
) S^y (t) = sin (! 0 t) S^1 (0) cos (! 0 t) S^2 (0) (5.92)
D E D E
S^x (t) = S^1 (0) cos (! 0 t) + S^2 (0) sin (! 0 t)
D E D E D E
) S^x (t) = cos (! 0 t) S^1 (0) + sin (! 0 t) S^2 (0) (5.93)
When the particle is initially in the state

j (0)i = j+Xi ;
we have
D E
S^z (0) = h (0)j S^z j (0)i = h+Xj S^z j+Xi = 0;
D E
S^y (0) = h (0)j S^y j (0)i = h+Xj S^y j+Xi = 0;
D E ~
S^x (0) = h (0)j S^x j (0)i = h+Xj S^x j+Xi = (5.94)
2
so that D E
S^z (t) = C ) C = 0; (5.95)
D E D E D E
S^y (t) = sin (! 0 t) S^1 (0) cos (! 0 t) S^2 (0)
D E
) S^2 (0) = 0; (5.96)
and
D E D E
S^x (t) = S^1 (0) cos (! 0 t) + S^2 (0) sin (! 0 t)
D E ~
) S^1 (0) = : (5.97)
2
Therefore, the expectation values become
D E D E ~ D E ~
S^z (t) = 0; S^y (t) = sin (! 0 t) ; S^x (t) = cos (! 0 t) (5.98)
2 2
which is in agreement with the results obtained in (e).
HW Prob. Precession of spin-1/2 particle in a magnetic …eld: Consider an

electron (charge, q = e and mass, m) with magnetic dipole moment
m:
~ Somebody turned on a uniform magnetic …eld B0 directed along the
positive y-axis.
(a) Determine the classical Hamiltonian
(b) Determine the quantum Hamiltonian
(c) Solve the eigenvalue equation for the quantum Hamiltonian
(d) Determine the state of the electron at a later time t if the initially state of
the electron, j (0)i = j Zi and j (0)i = j Xi :
(e) Using the state vector determined in (d) …nd the probabilities P+z (t) and
P z (t) ; P+x (t) and P x (t) for both initial states.
D E D E D E
(f ) Find the expectation values for S^z ; S^x ; and S^y when the electron
is initially in the state j (0)i = j Xi :
(g) Verify the results you determined in (f ) using the Heisenberg equation.
Example 3 Magnetic Resonance: The response of spin-1/2 particle inside an
atom or a molecule under the in‡uence of an oscillating external magnetic
…eld has been used for medical imaging. A spin-1/2 particle inside an
atom experiences an average local magnetic …eld, B~ 0 ; due to the electrons
in the neighboring atoms or molecules. By indirect measurement of this
magnetic …eld using a known oscillating external magnetic …eld, B ~ (t) ; one
can get an accurate information of the nature of the chemical bonding of
the atoms in the molecules surrounding the spin-1/2 particle. This tech-
nique which is commonly known as magnetic resonance Imaging (MRI)
has been used for medical imaging purposes.
Let the average local magnetic …eld due to the electrons in the neighboring
atoms be directed along the positive z-axis
~ 0 = B0 z^;
B (5.99)
and the external magnetic …eld oscillating with a frequency, ; magnetic

…eld is directed along the x-axis
~ = B1 cos ( t) x
B ^; (5.100)
so that the net magnetic …eld

~ = B0 z^ + B1 cos ( t) x
B ^: (5.101)
The quantum Hamiltonian due to the magnetic spin of the electron be-
comes
H^ = m
~ B ~ = ge B0 S^z + B1 cos ( t) S^x ; (5.102)
2me c
which we may write as

^ = ! 0 S^z + ! 1 cos ( t) S^x
H (5.103)
where
gqB0 gqB1
!0 = ; !1 = : (5.104)
2mc 2mc
(a) Find the matrix representation to the Schrödinger equation for this Hamil-
tonian in the Sz basis
(b) In the absence of the external magnetic …eld (! 1 = 0) solve the resulting
di¤erential equations.
(c) In the presence of external magnetic …eld determine the resulting di¤erential
equations and solve these equations for near resonance case !0 .
(d) By applying the result in part (c) determine the state vector at resonance
( = ! 0 ) for an initial state, j (0)i = j+Zi.
(e) Using the state vector in (d) determine the probabilities P+z and P z:
Solution:
(a) The Schrödinger equation
d ^ j (t)i
i~ j (t)i = H (5.105)
dt
using the completeness relation for the Sz basis
2
X
j+Zi h+Zj + j Zi h Zj = jan i han j = I; (5.106)
n=1
where ja1 i = j+zi and ja2 i = j zi ; can be rewritten as

2 2 2
d X X
^
X
i~ jan i han j (t)i = jam i ham j H jan i han j (t)i
dt n=1 m=1 n=1
2 2 X 2
d X X
^ jan i cn (t) jam i
) i~ cn (t) jan i = ham j H (5.107)
dt n=1 m=1 n=1
where
cn (t) = han j (t)i : (5.108)
Using matrices, one can write
d c1 (t) ^ ja1 i ha1 j H

ha1 j H ^ ja2 i c1 (t)
i~ = ^ ^ ja2 i : (5.109)
dt c2 (t) ha2 j H ja1 i ha2 j H c2 (t)
Now using the basis vectors

ja1 i = j+zi ; ja2 i = j zi ; (5.110)
and the Hamiltonian
^ = ! 0 S^z + ! 1 cos ( t) S^x
H (5.111)
one can write for the matrix
^ ja1 i ha1 j H
ha1 j H ^ ja2 i ^ j+Zi h+Zj H
h+Zj H ^ j Zi
^ ^ = ^ ^ j Zi
ha2 j H ja1 i ha2 j H ja2 i h Zj H j+Zi h Zj H
h+Zj S^z j+Zi h+Zj S^z j Zi
= !0
h Zj S^z j+Zi h Zj S^z j Zi
h+Zj S^x j+Zi h+Zj S^x j Zi
+! 1 cos ( t) : (5.112)
h Zj S^x j+Zi h Zj S^x j Zi
Using the results we obtained in the previous chapters for the matrix
representation of S^z and S^x in the z-basis, we have
h+Zj S^z j+Zi h+Zj S^z j Zi ~ 1 0
=
h Zj S^z j+Zi h Zj S^z j Zi 2 0 1
h+Zj S^x j+Zi h+Zj S^x j Zi ~ 0 1
= : (5.113)
h Zj S^x j+Zi h Zj S^x j Zi 2 1 0
so that
^ ja1 i ha1 j H
ha1 j H ^ ja2 i ~ !0 ! 1 cos ( t)
^ ja1 i ha2 j H
^ ja2 i = :
ha2 j H 2 ! 1 cos ( t) !0
Then the matrix representation for the Schrödinger equation becomes
d c+ (t) 1 !0 ! 1 cos ( t) c+ (t)
i = ; (5.114)
dt c (t) 2 ! 1 cos ( t) !0 c (t)
where we used
c1 (t) han j (t)i h+Zj (t)i c+ (t)
= = = (5.115)
c2 (t) han j (t)i h Zj (t)i c (t)
(b) In the absence of the external magnetic …eld (! 1 = 0); from

d c+ (t) 1 !0 ! 1 cos ( t) c+ (t)
i = ; (5.116)
dt c (t) 2 ! 1 cos ( t) !0 c (t)
we …nd the di¤erential equations.
d c+ (t) 1 !0 0 c+ (t)
i =
dt c (t) 2 0 ! 0 c (t)
dc+ (t) !0 dc (t) !0
) = i c+ (t) ; = i c (t) (5.117)
dt 2 dt 2
and the solution becomes

!0
i t
c (t) = a (0) e 2 : (5.118)
Then the state vector
j (t)i = c+ (t) j+Zi + c (t) j Zi (5.119)
becomes
!0 !0
i t i t
j (t)i = a+ (0) e 2 j+Zi + a (0) e 2 j Zi : (5.120)
If the initial state, j (0)i = j+Zi ; we have
a+ (0) = 1; a (0) = 0; (5.121)
and the state vector becomes

!0
i t
j (t)i = e 2 j+Zi : (5.122)
(c) In the presence of external magnetic …eld,
d c+ (t) 1 !0 ! 1 cos ( t) c+ (t)

i = ; (5.123)
dt c (t) 2 ! 1 cos ( t) !0 c (t)
leads to coupled …rst order di¤erential equations
dc+ (t) !0 !1
= i c+ (t) i cos ( t) c (t) ;
dt 2 2
dc (t) !1
= i cos ( t) c+ (t) + i! 0 c (t) : (5.124)
dt 2
From the solution we obtained in part (b) where there is no interaction

!0
i t
c (t) = a (0) e 2 ; (5.125)
one can make an educational assumption for the solution to the coupled
di¤erential equations !0
c (t) = a (t) e i 2 t ; (5.126)
d h !0
i !0 !0
a+ (t) e i 2 t = i a+ (t) e i 2 t
dt 2
!1 !0
i cos ( t) a (t) ei 2 t ;
2
d h !
i 20 t
i !1 !0
a (t) e = i cos ( t) a+ (t) e i 2 t
dt 2
!0
+i! 0 a (t) ei 2 t ; (5.127)
which leads to
d i
!0
t !0 i
!0
t
e a+ (t)
2 i a+ (t) e 2
dt 2
!0 ! 0 !1 !0
= i a+ (t) e i 2 t i cos ( t) a (t) ei 2 t
; (5.128)
2 2
d !1
) a+ (t) = i cos ( t) a (t) ei!0 t ;
dt 2
and
!0 d !0 !0
ei 2 t
a (t) + i a (t) ei 2 t
dt 2
!1 !0 !0
= i cos ( t) a+ (t) e i 2 t + i! 0 a (t) ei 2 t (5.129)
2
d !1
) a (t) = i cos ( t) a+ (t) e i!0 t (5.130)
dt 2
Using the relation
+e i t ei t
cos ( t) = (5.131)
2
the di¤erential equations can be rewritten as
d !1 h i
a+ (t) = i a (t) ei( +!0 )t + e i( ! 0 )t
;
dt 4
d !1 h i
a (t) = i a+ (t) e i( +!0 )t + ei( ! 0 )t
: (5.132)
dt 4
For near resonance case, ! 0 ; we can make the approximation
i( +! 0 )t i( ! 0 )t
e = 0; e =1 (5.133)
so that
d !1 d !1
a+ (t) = i a (t) ; a (t) = i a+ (t) : (5.134)
dt 4 dt 4
Taking the time derivative of these equations, we have
d2 !1 d !1 2
a+ (t) = i a (t) = a+ (t) : (5.135)
dt2 4 dt 4
and
d2 !1 d !1 2
a (t) = i a + (t) = a (t) : (5.136)
dt2 4 dt 4
so that one …nds the homogeneous second order di¤erential equations
d2 !1 2
2
a+ (t) + a+ (t) = 0 (5.137)
dt 4
and
d2 !1 2
2
a (t) + a (t) = 0; (5.138)
dt 4
the solution of which, from Theoretical Phys I, can be written as

!1 !1
a+ (t) = A cos t + B sin t ;
4 4
!1 !1
a (t) = C cos t + D sin t : (5.139)
4 4
Substituting this equations into
d !1 d !1
a+ (t) = i a (t) ; a (t) = i a+ (t) : (5.140)
dt 4 dt 4
we have
!1 !1 h !1 !1 i
A sin t + B cos t = i C cos t + D sin t ;
4 4 h 4 4 i
!1 !1 !1 !1
C sin t + D cos t = i A cos t + B sin t :
(5.141)
4 4 4 4
which leads to
A = iD; B = iC: (5.142)
The solutions can then be rewritten as
h !1 !1 i
a+ (t) = i D cos t C sin t ;
4 4
!1 !1
a (t) = C cos t + D sin t : (5.143)
4 4
Therefore, recalling that
!0
i t
c (t) = a (t) e 2 ; (5.144)
we may write the state vector
j (t)i = c+ (t) j+Zi + c (t) j Zi (5.145)
where
h !1 ! 1 i i !0 t
c+ (t) = i D cos t C sin t e 2 ;
h 4 4 i
!1 !1 !0
c (t) = C cos t + D sin t ei 2 t ; (5.146)
4 4
C and D are determined using the initial state.
(d) For an initial state j (0)i = j+Zi ;
h+Z j (0)i = 1; h Z j (0)i = 0 (5.147)
which means
h+Z j (t)ijt=0 = c+ (t) h+Z j+Zi + c (t) h+Z j Zijt=0 = 1
) iD = 1 ) D = i
h Z j (t)ijt=0 = c+ (t) h Z j+Zi + c (t) h Z j Zijt=0 = 0
) C=0 (5.148)
and
!1 i
!0
t !1 !0
c+ (t) = cos t e 2 ; c (t) = i sin t ei 2 t ; (5.149)
4 4
the state vector becomes
!1 i
!0
t !1 !0
j (t)i = cos t e 2 j+Zi i sin t ei 2 t j Zi : (5.150)
4 4
The probabilities, P+z and P z; will then be
2 !1
P+z = jh+Z j (t)ij = cos2 t ;
4
2 !1
P z = jh Z j (t)ij = sin2 t : (5.151)
4
Remark: Even when the external magnetic …eld is oscillating o¤ -resonance,

there is a …nite probability that the spin-half particle that is initially in the state
j+Zi can make a transition to the state j Zi : This probability can be determined
by solving the equations in Eq. (5.132) which I assigned as a homework problem.
This probability is given by
0q 1
2 2 =4
2 ! 2
=4 ( ! 0 ) + ! 1
P z = jh Z j (t)ij = 1
2 sin2 @ tA :
( ! 0 ) + ! 21 =4 2
(5.152)
which is known as Rabi’s formula.
HW: Reading
(a) One application of precession of spin-1/2 particle in a magnetic …eld is in
measurement of g from the equation
geB0
!0 = : (5.153)
2me c
for the Muon. Read the text and brie‡y summarize how precession of
spin-1/2 particle is used to experimentally measure g.
(b) Read the handout (from Feynman lecture) about the Ammonia molecule and
Ammonia maser. Write a summary of what you understood in relation to
what you have introduced about quantum mechanics up to this point.
Chapter 6
Interacting two spin-1/2

particles
In this chapter we will study the e¤ect of quantum interaction in a system made
of two sping-1/2 particles like the electron and proton in a hydrogen atom. In a
hydrogen atom there are one electron and one proton. The interaction between
these two particles is electrical as well as magnetic. However, in this chapter,
we will consider only e¤ects due to magnetic in order to make a connection with
what we were introduced in the preceding chapters. We will come back to the
electrical interaction in the second part of the course when we get into the wave
mechanics approach.
6.1 Two particle basis states

Let’s consider the general case of two interacting particle system. Let’s these
particles are a two particle state and the basis vectors describing the two states
for one of be fja1 i ; ja2 ig and for the other be fjb1 i ; jb2 ig : There exists four
basis vectors for the two interacting particles given by
j1i = ja1 i jb1 i = ja1 ; b1 i ;

j2i = ja1 i jb2 i = ja1 ; b2 i ;
j3i = ja2 i jb1 i = ja2 ; b1 i ;
j4i = ja2 i jb2 i = ja2 ; b2 i : (6.1)
As an example we shall consider two spin half particle described by spin up and
spin down in the z-direction fja1 i ; ja2 i = j+Zi ; j Zig and a spin one particle
described by horizontal and vertical polarization fjb1 i ; jb2 i = jhi ; jvig : The two
particle basis states for the spin half particles can then be written as
j1i = j+Z; +Zi ; j2i = j+Z; Zi ; j3i = j Z; +Zi ; j4i = j Z; Zi
143
144 CHAPTER 6. INTERACTING TWO SPIN-1/2 PARTICLES
and for the spin one particles

j1i = jh; hi ; j2i = jh; vi ; j3i = jv; hi ; j4i = jv; vi :
I would like to ephesize that this basis vectors are valid only when we consider
the spin or polarization degrees of freedom. For example if one includes the
position (which is a continuum state), for example, for the photon, the two
particle basis vectors becomes
Z Z
j1i = dx1 dx2 jx1 ; x2 ; h; hi ;
Z Z
j2i = dx1 dx2 jx1 ; x2 ; h; vi ;
Z Z
j3i = dx1 dx2 jx1 ; x2 ; v; hi ;
Z Z
j3i = dx1 dx2 jx1 ; x2 ; v; vi : (6.2)
The would also change if we add mode degrees of freedom.
6.2 The electron-proton spin interaction

The hydrogen atom is the best example for two spin half particle interaction
as it has only one proton and one electron. The most dominant interaction
between the electron and proton in a hydrogen atom is electrical resulting from
the charge. The classical Hamiltonian for the electron due to the coulombic
electrostatic interaction is given by
p2 p2 1 e2
H= + V (~r) = (6.3)
2me 2me 4 0 r
and the quantum Hamiltonian will then be
2
^ = p^ 1 e2 ~2 2 1 e2
H = r (6.4)
2me 4 0 r 2me 4 0 r
where r is the distance of the electron from the proton, me is the mass of the
electron, and e is the magnitude of the charge on the electron (proton). In spher-
ical coordinates a point in space (6.1) is described by the coordinates (r; ; ') :In
spherical coordinate one can write (from Theo Phys. I) the Laplacian, r2 ; as
1 @ @ 1 @ @ 1 @2
r2 = r2 + sin ( ) + 2 ;
r2 @r @r r2 sin ( ) @ @ r2 sin ( ) @'2
so that
~2 2 ~2 @ @ 1 @ @ 1 @2
r = 2
r2 + sin ( ) + 2
2me 2me r @r @r sin ( ) @ @ sin ( ) @'2
~2 2 ~2 @ @ 1 ^2
) r = r2 + L (6.5)
2me 2me r2 @r @r 2me r2
6.2. THE ELECTRON-PROTON SPIN INTERACTION 145
Figure 6.1: A point in space described by spherical coordinates, r; ; and ':
where we introduced an operator L^ (orbital angular momentum operator) de-

…ned by
^ 2 = ~2 1 @ @ 1 @2
L sin ( ) + 2 : (6.6)
sin ( ) @ @ sin ( ) @'2
Then the quantum Hamiltonian becomes
^ = ~2 @ @ 1 e2 1 ^2
H r2 L : (6.7)
2me r2 @r @r 4 0 r 2me r2
Upon solving the energy eigenvalue equation
^ jEi = E jEi
H
for this quantum Hamiltonian, one …nds the energy eigen values to be
me e4 1 13:6ev 2:18 10 18
J
En = = = ; (6.8)
8 20 h3 n2 n2 n2
where n = 1; 2; 3:::is known as the principal quantum number. As we will
see in Chapter...the solution to the energy eigenvalue equation also gives the
eigenvalues for the orbital angular momentum, l = 0; 1; 2:::n 1: The energy
spectrum for the electron in a Hydrogen is shown in Fig. 6.2
Figure 6.2: The energy levels for a Hydrogen atom. From left to right: the
electron is on the ground sate (n = 1), …rst excited state (n = 2), and …fth
excited state (n = 6). The transitions from the ground state to the excited
state requires photon absorption.
This energy spectrum of the electron in a hydrogen atom does not include
the week spin–spin (magnetic) interaction of the electron with the proton. Next
we will see the e¤ect of the spin-spin interaction between the electron and proton
in a Hydrogen atom. Suppose the additional quantum Hamiltonian due to this
interaction be H ^ I ; which is given by
! !
^ I = 2A S^1 S^2
H
~ 2
then when we include the spin-spin interaction,the total quantum Hamiltonian

becomes
H^ =H ^0 + HÎ ; (6.9)
where
^0 = ~2 @ @ 1 e2 1 ^2
H r2 L :
2me r2 @r @r 4 0 r 2me r2
Since h i
H^ 0; H
^ I = 0: (6.10)
we can apply the interaction picture
d Î j
i~ j I (t)i = H I (t)i (6.11)
dt
to determine the energy eigenvalues resulting due to the spin-spin interaction.
We will determine these eigenvalues using some of the methods we were

introduced in the previous chapters. To this end, we note that
! !
S^1 = S^1x x
^ + S^1y y^ + S^1z z^; S^2 = S^2x x
^ + S^2y y^ + S^2z z^ (6.12)
so that
! !
S^1 S^2 = S^1x S^2x + S^1y S^2y + S^1z S^2z : (6.13)
Using the raising and lowering operators for each particle
S^1 = S^1x iS^1y ; S^2 = S^2x iS^2y (6.14)
we have
1 ^ 1 ^
S^1x = S1+ + S^1 ; S^1y = S1+ S^1 ; (6.15)
2 2i
1 ^ 1 ^
S^2x = S2+ + S^2 ; S^2y = S2+ S^2 ; (6.16)
2 2i
so that
1 h^ ^ i
S^1x S^2x = S1+ S2+ + S^1 S^2 + S^1+ S^2 + S^1 S^2+ ;
4
1 h^ ^ i
S^1y S^2y = S1+ S2+ + S^1 S^2 S^1+ S^2 S^1 S^1+ ; (6.17)
4
and one can write

! ! 1h i
S^1 S^2 = S^1 S^2+ + S^1+ S^2 + 2S^1z S^2z : (6.18)
2
Then the quantum Hamiltonian for the spin-spin interaction part can expressed
as
h i
H^ I = A S^1 S^2+ + S^1+ S^2 + 2S^1z S^2z :
~2
Using the two spin half particles in the Sz basis, we determined earlier
j1i = j+Z; +Zi ; j2i = j+Z; Zi ; j3i = j Z; +Zi ; j4i = j Z; Zi (6.19)
^ I can be expressed as
the matrix representation for H
2 ^ I j1i h1j H
^ I j2i h1j H
^ I j3i h1j H
^ I j4i 3
h1j H
6 h2j H
^ I j1i h2j H
^ I j2i h2j H
^ I j3i h2j H
^ I j4i 7
HI = 6
4 h3j H
^ I j1i h3j H
^ I j2i h3j H
^ I j3i h3j H
^ I j4i
7
5 (6.20)
^ ^ ^
h4j HI j1i h4j HI j2i h4j HI j3i h4j H ^ I j4i
so that using
HI j1i = HI j+Z; +Zi

A h i
= 2 S^1 S^2+ j+Z; +Zi + S^1+ S^2 j+Z; +Zi + 2S^1z S^2z j+Z; +Zi
~
2A 2A ~ ~ A
= 2 S^1z S^2z j+Z; +Zi = 2 j+Z; +Zi = j+Z; +Zi
~ ~ 22 2
A
) HI j1i = j1i
2
A A
^ I j1i = h1 j1i = ; h2j H ^ I j1i = A h2 j1i = 0;
h1j H
2 2 2
^ A ^ A
h3j HI j1i = h3 j1i = 0; h4j HI j1i = h4 j1i = 0; (6.21)
2 2
HI j2i = HI j+Z; Zi
A h^ ^ i
= 2 S1 S2+ j+Z; Zi + S^1+ S^2 j+Z; Zi + 2S^1z S^2z j+Z; Zi
~
A 2 ~ ~ A
= 2 ~ j Z; +Zi + 2 j+Z; Zi = A j Z; +Zi j+Z; Zi
~ 2 2 2
A
) HI j2i = A j3i j2i
2
A
h1j HI j2i = A h1 j3i h1 j2i = 0;
2
^ I j2i = A h2 j3i A h2 j2i = A ;
h2j H
2 2
^ I j2i = A h3 j3i A ^ I j2i = A h4 j3i A h4 j2i = 0 (6.22)
h3j H h3 j2i = A; h4j H
2 2
HI j3i = HI j Z; +Zi
A h i
= 2 S^1 S^2+ j Z; +Zi + S^1+ S^2 j Z; +Zi + 2S^1z S^2z j Z; +Zi
~
A 2 ~ ~ A
= 2 ~ j+Z; Zi + 2 j Z; +Zi = A j+Z; Zi j Z; +Zi
~ 2 2 2
A A
) HI j3i = A j2i j3i ) h1j HI j3i = A h1 j2i h1 j3i = 0;
2 2
A
h2j HI j3i = A h2 j2i h2 j3i = A;
2
A A A
h3j HI j3i = A h3 j2i h3 j3i = ; h4j HI j3i = A h4 j2i h4 j3i = 0
2 2 2
(6.23)
HI j4i = HI j Z; Zi
A h i
= 2 S^1 S^2+ j Z; Zi + S^1+ S^2 j Z; Zi + 2S^1z S^2z j Z; Zi
~
A ~ ~ A
= 2 2 j Z; Zi = j Z; Zi ;
~ 2 2 2
A
) HI j4i = j4i ;
2
A A
h1j HI j4i = h1 j4i = 0; h2j HI j4i = h2 j4i = 0;
2 2
A A A
h3j HI j4i = h3 j4i = 0; h4j HI j4i = h4 j4i = ; (6.24)
2 2 2
one …nds for the matrix
2 A
3
2 0 A 0
6 0 A
A 0 7
HI = 6
4 0
2 7: (6.25)
A A
2 0 5
A
0 0 0 2
The eigenvalue equation

^ I jEI i = EI jEI i
H (6.26)
using the completeness relation for the two particle basis state vectors
j+Z; +Zi h+Z; +Zj + j+Z; Zi h+Z; Zj + j Z; +Zi h Z; +Zj

+ j Z; Zi h Z; Zj = I (6.27)
or
j1i h1j + j2i h2j + j2i h2j + j4i h4j = I (6.28)
or
2
X
jan ; bm i han ; bm j = I
n;m=1
) ja1 ; b1 i ha1 ; b1 j + ja1 ; b2 i ha1 ; b2 j + ja2 ; b1 i ha2 ; b1 j

+ ja2 ; b2 i ha2 ; b2 j = I (6.29)
one can write

2
X 2
X
^ I jan ; bm i han ; bm jEI i
jan0 ; bm0 i han0 ; bm0 j H
n;m=1 n0 ;m0 =1
2
X
= EI jan ; bm i han ; bm jEI i : (6.30)
n;m=1
Using matrices this can be put in the form

2 ^ I j1i ^ I j2i ^ I j3i h1j H
^ I j4i 32 3
h1j H h1j H h1j H h1j EI i
6 h2j H
^ I j1i ^ I j2i
h2j H ^
h2j HI j3i h2j H^ I j4i 7 6 h2j EI i 7
6 76 7
4 h3j H
^ I j1i ^ I j2i
h3j H ^
h3j HI j3i h3j H^ I j4i 5 4 h3j EI i 5
^ I j1i
h4j H ^ I j2i
h4j H ^ I j3i h4j H
h4j H ^ I j4i h4j EI i
2 3
h1j EI i
6 h2j EI i 7
= EI 6
4 h3j EI i 5
7 (6.31)
h4j EI i
where
j1i = ja1 ; b1 i = j+Z; +Zi ; j2i = ja1 ; b2 i = j+Z; Zi ;

j3i = ja2 ; b1 i = j Z; +Zi ; j4i = ja2 ; b2 i = j Z; Zi : (6.32)
Using the result we obtained for the matrix of the Hamiltonian, we have
2 A 32 3 2 3
2 0 A 0 h1j EI i h1j EI i
6 0 A
A 0 7 6 7 6 7
6 2 7 6 h2j EI i 7 = EI 6 h2j EI i 7 : (6.33)
4 0 A A
0 5 4 h3j EI i 5 4 h3j EI i 5
2
A h4j EI i h4j EI i
0 0 0 2
and using the identity matrix, one can put this equation in the form
2 A 32 3
2 EI 0 A 0 h1j EI i
6 0 A
EI A 0 7 6 h2j EI i 7
6 2 76 7
4 0 A A
EI 0 5 4 h3j EI i 5 = 0: (6.34)
2
A h4j EI i
0 0 0 2 EI
There follows that

A
2 EI 0 A 0
A
0 2 EI A 0
det A = 0; (6.35)
0 A 2 EI 0
A
0 0 0 2 EI
which leads to
A 3A
EI1 = EI2 = EI3 =; EI4 = ;: (6.36)
2 2
The corresponding eigenstates can easily be determined by substituting the
eigenvalues into the equation
2 A 32 3
2 EI 0 A 0 h1j EI i
6 0 A
EI A 0 7 6 h2j EI i 7
6 2 76 7
4 0 A A
EI 0 5 4 h3j EI i 5 = 0: (6.37)
2
A h4j EI i
0 0 0 2 EI
Figure 6.3: Fine and hyper…ne structure splitting in a Hydrogen atom.
These eigenvectors are found to be
1
jEI1 i = j+Z; +Zi ; jEI2 i = p [j+Z; Zi + j Z; +Zi] ; jEI3 i = j Z; Zi ;
2
1
jEI4 i = p [j+Z; Zi j Z; +Zi] :
2
Now to understand what exactly happened when we take into account the spin-
spin interaction of the proton and electron, let’s look at the energy spectrum
in the absence of this interaction We recall that the energy for the part of the
quantum Hamiltonian
^0 = ~2 @ @ 1 e2 1 ^2
H r2 L :
2me r2 @r @r 4 0 r 2me r2
is given by
me e4 1 13:6ev 2:18 10 18
J
En = = = : (6.38)
8 20 h3 n2 n2 n2
Therefore for each energy level, n, due to the spin-spin interaction there are two
possible values for the energy given by
^ =H
^0 + H
^ I ) E = En + EI = En + A2 ;
H
En 3A 2
This splitting of the each energy levels into two is known as the Hyper…ne split-
ting.
6.3 The addition of angular momenta

We are interested in the eigenstates and the eigenvalue for two spin half particle.
That means we are interested in solving
S^2 js; mi = ~2 s (s + 1) js; mi ; S^z js; mi = ~m js; mi ; (6.39)
where
! !
S^1 = S^1x x
^ + S^1y y^ + S^1z z^; S^2 = S^2x x
^ + S^2y y^ + S^2z z^
! ! ! ! ! !
) S^2 = S^1 + S^2 S^1 + S^2 = S^12 + S^22 + 2S^1 S^2 ; (6.40)
and
S^z = S^1z + S^2z :
We recall that for single spin-half particle
S^12 js1 ; m1 i = ~2 s1 (s1 + 1) js1 ; m1 i ; S^z1 js1 ; m1 i = ~m1 js1 ; m1 i ; (6.41)
and
S^22 js2 ; m2 i = ~2 s2 (s2 + 1) js2 ; m2 i ; S^z1 js2 ; m2 i = ~m1 js2 ; m2 i ; (6.42)
where
1 ^ 1 1
si = ; Szi = ;
2 2 2
for particle i = 1 or 2
! !
S^1 S^2 = S^1x S^2x + S^1y S^2y + S^1z S^2z : (6.43)
Homework: Show that

! ! ! !
S^2 ; S^1 S^2 = 0; S^z ; S^1 S^2 = 0: (6.44)
! !
Since both S^2 and S^z commute with S^1 S^2 ; these operators must have the
! !
same eigenstates. We have already determined the eigenstates for S^1 S^2 in the
previous section
8 9
< j+Z; +Zi ; =
A
Triplets = j Z; Zi ; EI1 = EI2 = EI3 = 2 ;
: p1 [j+Z; Zi + j Z; +Zi] ;
2
1 3A
Singlet = p [j+Z; Zi j Z; +Zi] ; EI4 = : (6.45)
2 2
6.3. THE ADDITION OF ANGULAR MOMENTA 153
which we may also write as

8 1 1 9
< 2; 2 ; =
1 1 A
Triplets = 2; 2 ; EI1 = EI2 = EI3 = 2 ;
: p1 1 ; 1 1 1 ;
2 2 2 + 2; 2 ;
1 1 1 1 1 3A
Singlet = p ; ; ; EI4 = : (6.46)
2 2 2 2 2 2
Noting that s1 = s2 = 1=2; we …nd
1 1 1 1 1 1 1 1 3~2 1 1
S^12 ; = S^22 ; = ~2 +1 ; = ;
2 2 2 2 2 2 2 2 4 2 2
1 1 1 1 1 1 1
S^z1 ; = S^z2 ; =~ ; (6.47)
2 2 2 2 2 2 2
Also we recall
! ! 1h i
S^1 S^2 = S^1 S^2+ + S^1+ S^2 + 2S^1z S^2z : (6.48)
2
so that
! ! 1 1 1 h^ ^ i 1 1
S^1 S^2 ; = S1 S2+ + S^1+ S^2 + 2S^1z S^2z ;
2 2 2 2 2
8 ! ! 2
9
>
> S^1 S^2 + 21 ; + 12 = ~2 ~2 + 21 ; + 12 = ~4 + 12 ; + 12 >
>
>
> ! ! >
>
>
> ~2 >
>
>
> S^1 S^2 12 ; 12 = ~ ~ 1
2;
1
2 = 4
1
2;
1 >
>
>
> ! ! h 2 2 2i >
>
< =
S^1 S^2 1 ; 1 = 1 S^1 S^2+ 1 ; 1 + 2S^1z S^2z 1 ; 1
2 2 2 2 2 2 2
) :
>
> = ~2 1 1 ~ ~ 1 1
= ~4
2
1 1 1 1 >
>
>
> 2 2; 2 + 2 h 2 2 2
; 2 2; 2 2; 2 i >
>
>
> ! ! >
>
>
> S1 S^2
^ 1 1 1 ^ ^ 1 1
+ 2S^1z S^2z 1 1 >
>
>
> 2 ; + 2 = 2 S1+ S2 2; +2 2; +2 >
>
: 2
~ 1 1 ~ ~ 1 1 ~2 1 1 1 1
;
= 2 2; 2 + 2 2 2; +2 = 4 2 2; 2 2; +2
(6.49)
Using the results above, …rst triplet state, for the total spin of the two particle
system, we have
! ! 1 1
S^2 js; mi = S^12 + S^22 + 2S^1 S^2 ;
2 2
1 1 1 1 ! ! 1 1
= S^12 ; + S^22 ; + 2S^1 S^2 ; (6.50)
2 2 2 2 2 2
we …nd
! !
1 1 3~2 3~2 ~2 1 1
S^2 js; mi = S^12 + S^22 + 2S^1 S^2
; = ~2 + + ;
2 2 4 4 2 2 2
1 1
) S^2 js; mi = ~2 1 (1 + 1) ; )s=1 (6.51)
2 2
For the z-component
1 1 1 1 1 1
S^z js; mi = S^1z + S^2z ; = S^1z ; + S^2z ; (6.52)
2 2 2 2 2 2
and using
1 1 1 1 1 1 1
S^1z ; = S^2z ; =~ ; (6.53)
2 2 2 2 2 2 2
we …nd
1 1 1 1 1 1
S^z js; mi = ~ + ; = ~ (1) ; )m=1 (6.54)
2 2 2 2 2 2
which indicates for a two spin-half particle system
1 1
j1; 1i = ; : (6.55)
2 2
For the second triplet,
! ! 1 1
S^2 js; mi = S^12 + S^22 + 2S^1 S^2 ;
2 2
1 1 1 1 ! ! 1 1
= S^12 ; + S^22 ; + 2S^1 S^2 ; (6.56)
2 2 2 2 2 2
using the relations we used, we …nd
! ! 1 1 3~2 3~2 ~2 1 1
S^2 js; mi = S^12 + S^22 + 2S^1 S^2 ; = ~2 + + ;
2 2 4 4 2 2 2
1 1
) S^2 js; mi = ~2 1 (1 + 1) ; )s=1 (6.57)
2 2
For the z-component
1 1 1 1 1 1
S^z js; mi = S^1z + S^2z ; = S^1z ; + S^2z ; (6.58)
2 2 2 2 2 2
we …nd
1 1 1 1 1 1
S^z js; mi = ~ ; = ~ (1) ; )m= 1 (6.59)
2 2 2 2 2 2
which leads to
1 1
j1; 1i = ; : (6.60)
2 2
6.3. THE ADDITION OF ANGULAR MOMENTA 155
For the third triplet
1 1
1 1 1 1 1 1 1 1
S^2 js; mi = S^12 p ; + ; + S^22 p ; + ;
2 2
2 2 2 2 2 2 2 2
!
! 1 1 1 1 1
+2S^1
S^2 p ; + ;
2 2 2 2 2
3~2 3~2 1 1 1 1 1
= + p ; + ;
4 4 2 2 2 2 2
~2 1 1 1 1 ~2 1 1 1 1
+ 2 ; ;+ + 2 ; ;
2 2 2 2 2 2 2 2 2 2
3~2 3~2 ~2 1 1 1 1 1
= + + p ; + ;
4 4 2 2 2 2 2 2
1 1
) S^2 js; mi = ~2 1 (1 + 1) ; )s=1 (6.61)
2 2
and
1 1 1 1 1 1 1 1 1 1
S^z js; mi = S^1z p ; + ; + S^2z p ; + ;
2 2 2 2 2 2 2 2 2 2
1 ~ 1 1 ~ 1 1 ~ 1 1 1 ~ 1 1
) S^z js; mi = p ; ; p ; + ;
2 2 2 2 2 2 2 2 2 2 2 2 2 2
1 1 1 1 1
) S^z js; mi = ~ (0) p ; + ; )m=0 (6.62)
2 2 2 2 2
There follows that

1 1 1 1 1
j1; 0i = p ; + ; : (6.63)
2 2 2 2 2
For the singlet
1 11 1 1 1 1 1 1 1
S^2 js; mi = S^12 p ; ; + S^22 p ; ;
2 22 2 2 2 2 2 2 2
!! 1 1 1 1 1
+2S^1
S^2 p ; ;
2 2 2 2 2
3~2 3~2 1 1 1 1 1
= + p ; ;
4 4 2 2 2 2 2
~2 1 1 1 1 ~2 1 1 1 1
+ 2 ; ; 2 ; ;+
2 2 2 2 2 4 2 2 2 2
3~2 3~2 3~2 1 1 1 1 1
= + p ; ;
4 4 2 2 2 2 2 2
1 1
) S^2 js; mi = ~2 0 (0 + 1) ; )s=0 (6.64)
2 2
and
1 1 1 1 1 1 1 1 1 1
S^z js; mi = S^1z p ; ; + S^2z p ; ;
2 2 2 2 2 2 2 2 2 2
1 ~ 1 1 ~ 1 1 ~ 1 1 1 ~ 1 1
) S^z js; mi = p ; + ; p ; ;
2 2 2 2 2 2 2 2 2 2 2 2 2 2
1 1 1 1 1
) S^z js; mi = ~ (0) p ; ; )m=0 (6.65)
2 2 2 2 2
There follows that

1 1 1 1 1
j0; 0i = p ; ; : (6.66)
2 2 2 2 2
The eigenvalue equation
S^2 js; mi = ~2 s (s + 1) js; mi ; S^z js; mi = ~m js; mi ; (6.67)
for two interacting spin-half systems we determined that there are three spin-one
triplet states
1 1
j1; 1i = ; ; (6.68)
2 2
1 1 1 1 1
j1; 0i = p ; ; ; (6.69)
2 2 2 2 2
1 1
j1; 1i = ; (6.70)
2 2
and
1 1 1 1 1
j0; 0i = p ; ; (6.71)
2 2 2 2 2
which is a spin-zero singlet state.
Chapter 7
Wave mechanics in one

dimension
In this chapter we will cover three parts. In the …rst part we will focus on
the mathematical techniques for transition from the bra-ket formalism of quan-
tum mechanics to wave formalism. In the second part we will learn how the
experimental realization of the dual nature of matter (particle and wave) led
Shröudinger to his famous equation. In the third part we will apply the SE to
1-D classic quantum problems.
7.1 From bra-ket vector to wave function

In order to make the transition from bra-ket formalism to wave formalism, we
shall consider a free particle in one dimension. Consider a free particle with
momentum p and position x. The position and momentum eigenvalue equation
for a free particle can then be written as
x
^ jxi = x jxi ; p^ jpi = p jpi : (7.1)
Since position and momentum are continuum, the orthonormality relation for
the eigenstates should be written as
hx0 jxi = (x0 x) ; hp0 jpi = (p0 p) ; (7.2)
with the corresponding completeness relation

Z Z
dx jxi hxj = I; dp jpi hpj = I:
For a free particle, the quantum Hamiltonian can be expressed as

2
^ = p^ :
H
2m
157
158 CHAPTER 7. WAVE MECHANICS IN ONE DIMENSION
We recall the Schrödinger equation

d ^ j (t)i
i~ j (t)i = H (7.3)
dt
Multiplying this equation by the bra vector hxj from the left
d ^ j (t)i
i~ hxj j (t)i = hxj H (7.4)
dt
which can also be rewritten as
@ ^ j (t)i
i~ hx j (t)i = hxj H (7.5)
@t
Using the completeness relation for position eigenstates, one can express
Z Z 2
^ j (t)i = hxj H
hxj H ^ dx0 jx0 i hx0 j (t)i = dx0 hxj p^ jx0 i hx0 j (t)i
2m
Z 2 Z 2
^ j (t)i = p^ p^
) hxj H dx0 hxj x0 i hx0 j (t)i = dx0 (x0 x) hx0 j (t)i
2m 2m
2
) hxj H^ j (t)i = p^ hxj (t)i = H ^ hxj (t)i
2m
There follows that
@ ^ hxj @ ^ (x; t)
i~ hx j (t)i = H (t)i ) i~ (x; t) = H (7.6)
@t @t
where we de…ned the function
(x; t) = hxj (t)i
which is known as the wave function.
7.2 The dual particle-wave nature of matter

In 1923 de Broglie suggested that the dual wave-particle nature of radiation
should have its counterpart in a dual particle-wave nature of matter. He stated
particles should have wave properties under certain circumstances and their
wave length is given by
h
= ; (7.7)
p
where p is the momentum of the particle and h is Planck’s constant. The exper-
imental observation of de-Broglie wave nature of particles was made by di¤erent
scientists using electrons. A wonderfully instructive experiment on electron dif-
fraction by double slit was carried out by A. Tonomura. The experimental
set-up is shown below. Electrons emitted from a source are sent to the electron
biprism. The biprism is made of two parallel plates, with a thin …lament (1mm
7.2. THE DUAL PARTICLE-WAVE NATURE OF MATTER 159
in diameter) in between. When the …lament is grounded, the electrons pass

on both sides of the …lament and hit the detector with a uniform distribution.
When a positive voltage is applied to the …lament, the electrons on the two
sides are de‡ected by the …lament and the biprism forms the equivalent of a
double-slit. The electrons are attracted towards the central …lament and over-
lap in the electrons arrived lower detector plane at the detector are displayed as
bright spots on the monitor. Even when the electron arrival rate is as low as 10
electrons/sec, the accumulation of single electrons forms a biprism interference
pattern.
The pattern of the hits of electrons on the absorbing screen slowly builds up
Figure 7.1: Two slit interference.
to a wavelike interference pattern similar to that of a two-slit experiment for

photons. This is a clear indication of the wave property of the electron which is
manifested by the interference pattern. We thus expect that an electron must
describe by a wave function, traditionally denoted by (~r; t) : In order to get
an electron to interfere with itself we must insist that (x; t) obeys a linear
equation. In that case, a sum of two wave functions is also a wave function, so
that the superposition rules apply. Further more, we expect that predictability
of where an electron hits will be replaced by a statement, involving the wave
function (~r; t), about the probability that an electron arrives at ~r: This chapter
is devoted to the arguments that lead to the correct form of the linear equation
obeyed by (~r; t) ; the probability for …nding the electron at ~r at time t in terms
of (~r; t), and other general properties of the wave function.
Generally, what is understand from this experiment is that a if a source S
emits independent particles, one at a time. The particles fall on a screen drilled
with two holes H1 and H2 as shown in Fig. 7.1. In the experiment, a detector
measures the detection rate N (y) as a function of its y position. The record of
N (y) displays an interference pattern, which can only be interpreted by invoking
a wave passing through both holes.
7.3 Plane waves and wave packets

A wave is characterized by its wave length (or the wave number k = 2 = ),
frequency frequency (or angular frequency ! = 2 ), and its velocity, ~v . If
experiment proved that particle can behave like waves under some conditions,
we must be able to describe this behavior using some kind of wave function,
(~r; t) that satis…es some speci…c requirements. We shall consider …rst a speci…c
7.3. PLANE WAVES AND WAVE PACKETS 161
type of a wave function that we commonly encounter- the plane wave. Let this
plane wave is propagating along the positive x-direction which means the wave
function is independent of the coordinates y and z since it is a plane wave and
is propagating along the positive x-axis. The function can be expressed as
k (x; t) = A1 cos (kx !t) + A2 sin (kx !t) (7.8)
or equivalently
k (x; t) = A exp [i (kx !t)] + B exp [ i (kx !t)] : (7.9)
We will come back to the more general complex function form of the wave func-
tion. In order to relate the experimental observation in double-slit interference
pattern, let’s consider a simple normalized sinusoidal wave function at t = 0
described by
1
k (x; t) = p sin (kx) (7.10)
Suppose we consider a …nite number of this function with di¤erent values for k
(wavelength) given by
2
k= = n; (7.11)
one can then write

8 P1
>
> cos (nx) ;
X < Pk=1
10
cos (nx)
(x; t) = k (x; t) = Pk=1
100 (7.12)
>
> k=1 cos (nx)
k : P1000
k=1 cos (nx)
and 8 hP i2
>
> 1
cos (nx) ;
>
> k=1
>
> hP i2
>
< 10
2 k=1 cos (nx)
j (x; t)j = (x; t) (x; t) = hP i2 : (7.13)
>
> 100
cos (nx)
>
> k=1
>
> h i2
: P1000 cos (nx)
>
k=1
Now let’s examine the graphs for these functions. For a wave function
(x; t) = cos (x) (7.14)
for
(x; t) = cos (x) + cos (2x) + cos (3x) (7.15)
and for
(x; t) = cos (x) + cos (2x) + cos (3x) + cos (4x) + cos (5x) + cos (6x)
cos (7x) + cos (8x) + cos (9x) + cos (10x)
We can see from the three …gures above that adding several waves of di¤erent
wavelength together will produce an interference pattern that resemble the two
particle interference pattern observed in a double-slit experiment. This pattern
shows that the interference begins to localize the wave. But that process spreads
the wave number (k = 2 = ) as the average wave length becomes shorter as one
can see in Fig.7.2. From the observations made in the …gures above and the
Figure 7.2: Interference and uncertainty principle.
experimental results for the wave nature of particles we can say that the wave
function for a particle can be described by an in…nite number of plane waves that
di¤er only by their wavelength (or by their wave number k). The superposition
of these waves for a …nite number of them can then generally be expressed as
X
(x; t) = A (k) ei(kx !t) = (x) (t) (7.16)
k
where X
(x) = A (k) eikx ; (t) = e i!t
k
7.3. PLANE WAVES AND WAVE PACKETS 163
where A (k) is the amplitude which contains the information about the distrib-
ution of the wave number. Now if we consider in…nite number of these waves, if
these wave number di¤er by an in…nitessimal interval ( k ! 0) one can write
the wavefunction by
Z 1
(x; t) = A (k) ei(kx !t) dk = (x) (t) (7.17)
1
such function represent a wave packet.
A Gaussian wave packet: We consider the distribution of the wave number
k, is described by a Gaussian function
(k k0 )2 =2
A (k) = e (7.18)
which is centered about the value k0 : The wave packet at the initial time, t = 0,
becomes Z 1
(k k0 )2 =2 ikx
(x; 0) = e e dk (7.19)
1
Introducing the change of variable
q=k k0 ) k = q + k0 ; ) dq = dk (7.20)
we have
Z 1 Z 1
2iq
(x; 0) = e q 2 =2 i(q+k0 )x
e dq = eik0 x e 2 (q 2 x)
dq
1 1
Z 1 Z 1
2iq x2
2 q2 x 2
(q ix 2
) dq
= eik0 x x =2 e 2 2
dq = eik0 x x =2 e 2
1 1
Z 1
x2 =2 02
) (x; 0) = eik0 x e 2 q dq 0 (7.21)
1
Using the relation r

Z 1
2 2
exp[ x ]dx =
1 2
we …nd
r r
2 ik0 x x2 =2 2 x2 =2
(x; 0) = e e = e eik0 x
) (x; 0) = B (x) eik0 x : (7.22)

where r
2 x2 =2
B (x) = e :
This is also a plane-wave factor characterized by the wave number k0 and mod-
ulating function that acts to localize the packet about x = 0. Let’s look at the
width of the two packets by considering the square of the Gaussian distributions
2 (k k0 )2 2 x2 =
jA (k)j = e ; j (x)j = e : (7.23)
The width is the de…ned as the full width of the distributions at approximately
1=3 of the maximum values. This happens when
2 2
(k k0 ) ' 1; (x 0) = ' 1 (7.24)
which give the full width
p p
k = 2= ; x = 2 : (7.25)
Now we note that the product of the two
k x=4 (7.26)
which is independent of which in fact, as we shall see later, is always
1
k x> : (7.27)
2
7.4. THE SCHRÖDINGER EQUATION 165
Example 1 Consider a wave packet for which
N K k K
A (k) = (7.28)
0 elesewhere
and calculate (x; 0) ; and use some reasonable de…nition for the width
to show that the relation
1
k x> : (7.29)
2
is satis…ed.
Solution: For the initial time the wave packet is given by
Z 1
(x; 0) = A (k) eikx dk (7.30)
1
which leads to
Z K
2N sin (Kx)
(x; 0) = N eikx dk = : (7.31)
K x
2
For jA(k)j the full width at 1=3 of the maximum value is
k = 2K: (7.32)
On the other hand, from result for (x; 0), the distribution for x is
2
2 sin (Kx)
j (x)j = (7.33)
x
and a reasonable de…nition of x might be the distance between the two
points at which (x) …rst vanishes as it goes away from x = 0: [See Fig.
??] Since (x) vanish when
Kx = (7.34)
the width is found to be

2
) : x= (7.35)
K
Therefore the product of the two width becomes
1
k x=4 > : (7.36)
2
7.4 The Schrödinger equation

We recall the wave packet
Z 1
(x; t) = A (k) ei(kx !t)
dk; (7.37)
1
which describes a free traveling electron in the positive direction. We now make
the connection to real physical system. To this end, we recall the de Broglie
wave length
h 1 h ~
= ) = = = ) k = p=~ (7.38)
p k 2 2 p p
which is related to the momentum and
E
E = ~! ) ! = (7.39)
~
which relates energy and frequency. Using these relations we may express a
wave packet for a particle with momentum p and energy E as
Z 1 Z 1
p i(px Et)=~ p 1 p i(px Et)=~
(x; t) = A e d = A e dp: (7.40)
1 ~ ~ 1 ~ ~
Replacing
1 p 1
A =p (p) (7.41)
~ ~ 2 ~
we may write Z 1
1
(x; t) = p (p) ei(px Et)=~ dp: (7.42)
2 ~ 1
Now let’s di¤erentiate this expression …rst with respect to time
Z 1
@ E 1
(x; t) = i p (p) ei(px Et)=~ dp
@t ~ 2 ~ 1
Z 1
@ 1
) i~ (x; t) = E p (p) ei(px Et)=~ dp
@t 2 ~ 1
@
) i~ (x; t) = E (x; t) : (7.43)
@t
Di¤erentiating with respect to x twice leads to
Z 1
@ i 1
(x; t) = p (p) pei(px Et)=~ dp
@x ~ 2 ~ 1
Z 1
@2 1 1
) (x; t) = p (p) p2 ei(px Et)=~ dp
@x2 ~2 2 ~ 1
Z 1
@2 1
) ~2 2 (x; t) = p (p) p2 ei(px Et)=~ dp: (7.44)
@x 2 ~ 1
Multiplying both sides by (1=2m) ; we …nd
Z 1
~2 @ 2 1 p2 i(px Et)=~
(x; t) = p (p) e dp (7.45)
2m @x2 2 ~ 1 2m
We recall that the wave function
Z 1
1
(x; t) = p (p) ei(px Et)=~
dp: (7.46)
2 ~ 1
7.4. THE SCHRÖDINGER EQUATION 167
is the wave function of a free particle and the total energy E is just the kinetic
energy. Therefore
p2 p2
E= ) E (x; t) = (x; t) : (7.47)
2m 2m
If we replace
@
p! i~
@x
we may write
Z 1
p2 1 p2 i(px Et)=~
E (x; t) = (x; t) = p (p) e dp (7.48)
2m 2 ~ 1 2m
Therefore
@ ~2 @ 2
i~ (x; t) = (x; t) = E (x; t) (7.49)
@t 2m @x2
which is the Schrödinger equation for a free particle. We can generalize the
energy equation in the presence of a potential, V (x)
p2
E= + V (x) (7.50)
2m
as
@ ~2 @ 2
i~ (x; t) = + V (x) (x; t) : (7.51)
@t 2m @x2
This is the equation that we will be working with through out this chapter. For
the case
(x; t) = (x) (t)
and the potential does not depend on time, one can easily …nd
~2 d2
+ V (x) (x) = E (x)
2m dx2
The Heisenberg Uncertainty relation: recalling that k = p=~, the relation we

derived earlier
1
k x> : (7.52)
2
takes the form
~
p x> : (7.53)
2
This means that (x) can not describe a particle that is both well-localized in
space and has a sharp momentum at the same time.
7.5 The probability interpretation of the wave

function
We recall that for a two particle state like the spin-half particle described by
the state vector
j (t)i = c+ j+Zi + c j Zi (7.54)
the probability for the measurement of the spin of the particle be +Z is given
by
2
P+ (t) = jh+Zj (t)ij : (7.55)
One can then make the interpretation that
2 2
P+ (t) = jhxj (t)ij dx = hxj (t)i h (t)j xi dx = j (x; t)j dx: (7.56)
the probability of …nding a particle described by the wave function (x; t) in

the region lying between x and x + dx is given by
2
P (x; t) dx = j (x; t)j dx (7.57)
If the wave packet spreads with time, what it means for the probability given
above is that if the particle is known to be in a certain region with some prob-
ability distribution, with increasing time, will have an increasing probability of
being found outside that region.
Since the particle is somewhere in the region 1 < x < 1; the probability
of …nding the particle somewhere in this region is always one. That means the
relation Z 1 Z 1
2
P (x; t) dx = j (x; t)j dx = 1 (7.58)
1 1
along with the linearity of the Schrödinger equation (if (x; t) is a solution to
the Schrödinger equation, so does the function A (x; t)) is used to normalize
the wave function. The initial wave function must be square integrable,
Z 1
2
j (x; 0)j dx < 1 (7.59)
1
This require the wave function (x; 0) to go to zero rapidly as x ! 1:The

2
phase is important in the probability j (x; 0)j dx: As an example consider the
two slit experiment where the wave function expressed as
= R1 ei 1
+ R2 ei 2 : (7.60)
The probability density

2 2 2 2
j j = R1 ei 1
+ R2 ei 2
= jR1 j + jR1 j + 2R1 R2 cos ( 1 2) (7.61)
depends on the relative phase.

7.5. THE PROBABILITY INTERPRETATION OF THE WAVE FUNCTION169
The probability Current: we start from the probability density

2
P (x; t) = j (x; t)j = (x; t) (x; t) (7.62)
and di¤erentiate with respect to time

@ @ @
P (x; t) = (x; t) (x; t) + (x; t) (x; t) (7.63)
@t @t @t
Using the Schrödinger equation
@ ~2 @ 2
i~ (x; t) = + V (x) (x; t) (7.64)
@t 2m @x2
along with its complex conjugate
@ ~2 @ 2
i~ (x; t) = + V (x) (x; t) (7.65)
@t 2m @x2
we may write
@ ~2 @2
i~ (x; t) (x; t) = (x; t) 2 (x; t)
@t 2m @x
+V (x) (x; t) (x; t) (7.66)
and
@ ~2 @2
i~ (x; t) (x; t) = (x; t) 2 (x; t)
@t 2m @x
+V (x) (x; t) (x; t) (7.67)
so that subtracting the two equations, we …nd

@ @
i~ (x; t) (x; t) + (x; t) (x; t)
@t @t
~2 @2 @2
= (x; t) (x; t) (x; t) 2 (x; t) : (7.68)
2m @x2 @x
Using
@ @ @
P (x; t) = (x; t) (x; t) + (x; t) (x; t) (7.69)
@t @t @t
we may write
@ ~ @2 @2
i P (x; t) = (x; t) 2 (x; t) (x; t) 2 (x; t)
@t 2m @x @x
~ @ @ @
= (x; t) (x; t) (x; t) (x; t)
2m @x @x @x
~ @ @ @
= (x; t) (x; t) (x; t) (x; t) : (7.70)
2mi @x @x @x
If we de…ne the probability current, J (x; t)as

~ @ @
J (x; t) = (x; t) (x; t) (x; t) (x; t) ; (7.71)
2mi @x @x
we have
@ @
P (x; t) = J (x; t) (7.72)
@t @x
so that integrating with respect to x over the entire space along x,
Z 1 Z 1
@ @ 1
P (x; t) dx = J (x; t) dx = J (x; t)j 1 (7.73)
@t 1 1 @x
Z 1 1
@ ~ @ @
P (x; t) dx = (x; t) (x; t) (x; t) (x; t) :
@t 1 2mi @x @x 1
(7.74)
recalling that the wave function must go to zero rapidly as x ! 1; we …nd
Z 1
@
P (x; t) dx = 0 (7.75)
@t 1
N.B. "The appearance of probability in quantum mechanics di¤ ers from its ap-
pearance in classical mechanics. Here it is not a statement of ignorance about
what is ’really" going on, as is the case when we speak of the probability of a
coin-toss leading to heads or tails, but it is a basic limitation on what we can
know when the wave function is known.
Example 2 Consider a two-slit experiment, in which the wave function at slit

1 acquires an arbitrary random phase that is to be averaged over, so that
the total wave function at the screen is
(x; t) = ei' 1 (x; t) + 2 (x; t) : (7.76)
Such situation might arise when there are two incoherent electron sources
one at each slit. Show that under these circumstances the interference
averages out.
Solution: We note that the probability density
2
P (x; t) = ei' 1 (x; t) + 2 (x; t)
2 2
=j 1 (x; t)j + j 1 (x; t)j + 2 cos (') Re ( 1 (x; t) 2 (x; t))
+2 sin (') Re ( 2 (x; t) 1 (x; t)) : (7.77)
If the phase, '; of the electron various randomly from electron to electron
the average value
hcos (')i = hsin (')i = 0 (7.78)
and we …nd
2 2
P (x; t) = j 1 (x; t)j + j 1 (x; t)j : (7.79)
7.6. EXPECTATION VALUES IN WAVE MECHANICS 171
Example 3 What is the probability current for a wave function of the form
(a)
(x; 0) = Aeikx + Be ikx
(7.80)
(b)
x
(x; 0) = Ae (7.81)
(c)
iS(x)=~
(x; 0) = R(x)e (7.82)
7.6 Expectation values in wave mechanics

The probability of …nding a particle in the region between x and x + dx is given
by
2
P (x; t) dx = j (x; t)j dx: (7.83)
The most probable value to a physically observable quantity described by the
variable, f (x) ; that is a function of the position x is denoted by hf (x)i an is
known as the expectation value and is given by
Z 1 Z 1
hf (x)i = f (x)P (x; t) dx = (x; t) f (x) (x; t) dx: (7.84)
1 1
which basically gives the most probable outcome of an experimental measure-

ment if one performs on the variable f (x):
I would like to determine this relation from a quantum system with discrete
states like spin-1/2 or spin one particle. We recall that the expectation value
for a physical observable represented by an operator A^ is given by
D E
A^ = h j A^ j i : (7.85)
For the operator A^ satisfying the eigenvalue equation

A^ jai = a jai
with N eigenvalues fa1 ; a2 ; a3 :::aN g and corresponding eigen vectors fja1 i ; ja2 i ; ja3 i ::: jaN ig ;
one can write the state vector, using the completeness relation, as
N
X N
X
j i= jan i han j i = cn jan i ;
n=1 n=1
where
cn (t) = han j j 0i
If the system is initially is in a state j 0 i at t = 0 and evolves with time, we
can express the state at a later time, t, as
N
X N
X
j i= ^ (t) j
jan i han j U 0i = cn (t) jan i :
n=1 n=1
where
^ (t) j
cn (t) = han j U 0i :
We have seen that the expectation value for the operator A;^ can be determined
using
D E XN
2
A^ = h j A^ j i = jcn (t)j an : (7.86)
n=1
Now let’s say we have another operator, F^ A^ ; function of the operator A;

^
using a series expansion one can write
2 3 2 3
^ ^ d2 F^ A^
1 4 dF A 5 1
F^ A^ = 1+ A^ + 4 5 A^2 + :::
1! dA^ 2! dA^2
^
A=0 ^
A=0
2 3
X1 d F^ A^
j
) F^ A^ = 4 5 A^n (7.87)
dA^j
j=0 ^
A=0
so that
2 3 2 3
1 dF^ A^ 1 d2 F^ A^
F^ A^ jai = 1 + 4 5 A^ jai + 4 5 A^2 jai + :::
1! dA^ 2! dA^2
^
A=0 ^
A=0
2 3 2 3
j ^ ^ j ^ ^
X d F A
1 X d F A
1
) F^ A^ = 4 5 A^j jai = 4 5 aj jai = F (a) :
dA^j dA^j
j=0 ^ j=0 ^
A=0 A=0
(7.88)
In view of this relation, one can then express
D E N
X N
X
F^ A^ = h j F^ A^ j i = h j F^ A^ jan i han j i = h j F (an ) jan i han j i
n=1 n=1
D E N
X N
X 2
) F^ A^ = F (an ) h j an i han j i = F (an ) jhan j ij
n=1 n=1
D E N
X 2
) F^ A^ = F (an ) jcn (t)j (7.89)
n=1
Now let’s consider a quantum system with continuum states. Suppose the phys-
ical observable represented by position. For one dimensional case, such as along
x, we may write A^ = x ^; F^ A^ = F^ (^
x) ; and the eigenvalue equation
^ jxi = x jxi ) F^ (^
x x) jxi = F (x) jxi (7.90)
7.7. WHERE THE MOMENTUM OPERATOR COME FROM? 173
Then the expectation value for F^ (^

x), using the completeness relation for posi-
tion eigenstates, Z 1
dx jxi hxj = I; (7.91)
1
one can be expressed as

D E Z 1
F^ (x) = h j F^ (^
x) j i = h j F^ (^
x) jxi hxj i
1
N
X Z 1 Z 1
2
= h j F (x) jxi hxj i = F (x) h j xi hxj i = F (x) jhxj ij
n=1 1 1
D E Z 1 Z 1
2
) F^ (x) = F (x) j (x; t)j = (x; t) F (x) (x; t) (7.92)
1 1
7.7 Where the momentum operator come from?

Since you were introduced to modern physics you have been told again and
again that the momentum operator in one dimension, for example x, is given
by
@
p^x = i~ ; (7.93)
@x
and in three dimension
! @ @ @
p^ = p^x i + p^x j + p^x k = i~ i +j +k = i~r:
@x @y @z
We use this operator to determine the operator for the kinetic energy, T^,
! !
p^ p^ ( i~r) ( i~r) ~2 2
T^ = = = r :
2m 2m 2m
As a physicist you might have wondered how the momentum operator is deter-
mined or where the heck it come from. Such kind of questions are questions
a physicist must ask. Next we will determine this operator. To this end, we
recalling that in classical mechanics the momentum of a free particle with mass
m in the x direction is expressible as
dx
px = m (7.94)
dt
we may write the expectation value of the momentum, in quantum mechanics,
as
d
h^
px i = m h^ xi : (7.95)
dt
Applying the relation, we derived above
D E Z 1
F^ (x) = (x; t) F (x) (x; t) : (7.96)
1
we have Z 1
h^
xi = (x; t) x (x; t) : (7.97)
1
so that one can express the momentum as
Z
d 1
h^
px i = m (x; t) x (x; t) dx
dt 1
Z 1 Z 1
@ @
=m x (x; t) (x; t) dx + x (x; t) (x; t) dx (7.98)
1 @t 1 @t
We note here the time dependence is carried by the wave function. The change
in x with respect to time is due to the change in the wave function. Using the
Schrödinger equation
@ ~2 @ 2
i~ (x; t) = + V (x) (x; t) (7.99)
@t 2m @x2
along with its complex conjugate
@ ~2 @ 2
i~ (x; t) = + V (x) (x; t) (7.100)
@t 2m @x2
we can write
Z 1
m ~2 @ 2
h^
px i = x (x; t) + V (x) (x; t) dx
1 i~ 2m @x2
Z 1
m ~2 @ 2
+ x (x; t) + V (x) (x; t) dx (7.101)
1 i~ 2m @x2
which simpli…es into
Z
~ 1 @2 @2
h^
px i = x (x; t) 2 (x; t) x (x; t) (x; t) dx:
2i 1 @x @x2
Using integration by parts,
Z Z
udv = uv vdu (7.102)
we …nd
Z 1 1
@2 @
x (x; t) (x; t) dx = x (x; t) (x; t)
1 @x2 @x 1
Z 1
@ @
[x (x; t)] (x; t) : (7.103)
1 @x @x
and
1
@2 @
x (x; t) (x; t) dx = x (x; t) (x; t)
@x2 @x 1
Z 1
@ @
[x (x; t)] (x; t) : (7.104)
1 @x @x
We know from the properties of the wave function that the wave function (x; 0)
must go to zero rapidly as x ! 1: As a result
Z 1 Z 1
@2 @ @
x (x; t) 2 (x; t) dx = [x (x; t)] (x; t)
1 @x 1 @x @x
Z 1
@ @
= x (x; t) + (x; t) (x; t) dx (7.105)
1 @x @x
Similarly
Z 1 Z 1
@2 @ @
x (x; t) 2 (x; t) dx = x (x; t) + (x; t) (x; t) dx:
1 @x 1 @x @x
(7.106)
Now substituting these two expressions into
Z
~ 1 @2 @2
h^
px i = x (x; t) 2 (x; t) x (x; t) (x; t) dx:
2i 1 @x @x2
we …nd
Z 1
i~ @ @ @
h^
px i = x (x; t) (x; t) + (x; t) (x; t)
2 1 @x @x @x
@ @ @
x (x; t) (x; t) (x; t) (x; t) dx:
@x @x @x
Z
i~ 1 @ @
) h^
px i = (x; t) (x; t) (x; t) (x; t) dx: (7.107)
2 1 @x @x
Once again applying integration by parts, we may write
Z 1 Z 1
@ 1 @
(x; t) (x; t) dx = (x; t) (x; t)j 1 (x; t) (x; t) dx
1 @x 1 @x
Z 1
@
= (x; t) (x; t) dx; (7.108)
1 @x
where we used the requirement that the wave function, (x; t) ; must go to zero
rapidly as x ! 1: Using this result we …nd for the expectation value of the
momentum
Z 1 Z 1
@ @
h^
px i = i~ (x; t) (x; t) dx = (x; t) i~ (x; t) dx:
1 @x 1 @x
(7.109)
or Z 1
h^
px i = (x; t) p^x (x; t) dx (7.110)
1
where we represented the di¤erential operator by the MOMENTUM OPERA-

TOR
@
i~ = p^x : (7.111)
@x
Note that the momentum operator is positioned after (x; t) and before (x; t) :
Generally, for operators, this position is very important and it must be preserved
for all operators.
One can easily show that
Z 1 2
@
p^2x = (x; t) i~ (x; t) dx: (7.112)
1 @x
and more generally

Z 1
hf (^
px )i = (x; t) f (^
px ) (x; t) dx: (7.113)
1
The commutation relation for x

^ and p^x : we consider the momentum operator
@
p^x = i~ (7.114)
@x
and another operator which is a function of the momentum operator and de…ned
as
@
x^px = i~x (7.115)
@x
Now we operate the …rst operator on the function which we de…ne in terms of
the wave function as x and the second operator on just the wave function ;
@ @
p^x (x ) = i~ (x ) = i~ +x ; (7.116)
@x @x
@
x^
px =; i~x (7.117)
@x
so that subtracting these two equations leads to
@ @
x^
px p^x x = i~x + i~ + i~x ) x^
p p^x = i~ : (7.118)
@x @x
There follows that the commutation relation for position and the corresponding
momentum
[x; p^] = x^
p p^x = i~: (7.119)
We have seen that the wave function for a free particle described by a wave
packet satis…es the Schrödinger equation. We have also seen that more generally
for a particle in a potential …eld, V (x) ; the wave function describing the particle
satis…es the Schrödinger equation
@ ~2 @ 2
i~ (x; t) = + V (x) (x; t) : (7.120)
@t 2m @x2
In this section we shall solve the Schrödinger equation when the potential is
independent of time (time-independent Schrödinger equation)
The relation between (p) and (x; 0): At the initial time t = 0, the wave
function becomes
Z 1
1
(x; 0) = p (p) eipx=~ dp: (7.121)
2 ~ 1
p0
Multiplying both sides by e i ~ x and integrating both sides with respect to x,
we have
Z 1 Z 1 Z 1
p0 1 p0
e i ~ x (x; 0) dx = p e i~x (p) eipx=~ dpdx; (7.122)
1 2 ~ 1 1
which we may rewrite as

Z 1 Z 1 Z 1
p0 1 p0 )x=~
e i ~ x (x; 0) dx = p (p) dp ei(p dx: (7.123)
1 2 ~ 1 1
so that using the relation (refer to Theoretical physic I )

Z 1
0
ei(p p )x=~ dx = 2 ~ (p p0 ) (7.124)
1
we …nd
Z 1 Z 1
0
i p~ x 1
e (x; 0) dx = p (p) 2 ~ (p p0 ) dp
1 2 ~ 1
Z 1
1 p0
) (p0 ) = p e i ~ x (x; 0) dx (7.125)
2 ~ 1
Example 4 Show that the expectation value of the momentum is always real
as the momentum represent a physical observable.
Solution: If the momentum operator is Hermitian, its expectation value must
be real. Therefore we need to show that
h^
px i h^
px i = 0 (7.126)
Using Z 1
@ (x; t)
h^
px i = (x; t) i~ dx: (7.127)
1 @x
we have
Z 1
@ (x; t)
h^
px i = (x; t) i~ dx
1 @x
Z 1
@ (x; t)
= i~ (x; t) dx
1 @x
Z 1
@
) h^
px i = (x; t) i~ (x; t) dx (7.128)
1 @x
so that
Z 1
@ (x; t) @
h^
px i h^
px i = i~ (x; t) + (x; t) (x; t) dx
1 @x @x
Z 1
@ (x; t) (x; t) 1
= i~ dx = i~ (x; t) (x; t)j 1 = 0
1 @x
h^ px i ) p^x = p^yx
px i = h^ (7.129)
7.8 The wave function and the momentum space

We have seen the relation between the wave function at the initial time (x)
and the function (px ) which is given by
Z 1
1 px
(px ) = p e i ~ x (x) dx: (7.130)
2 ~ 1
We now discuss the physical meaning of the function (px ) : To this end, we
note that
Z 1 Z 1 Z 1
1 px
(px ) (px ) dpx = (px ) p e i ~ x (x) dxdpx
1 1 2 ~ 1
Z 1 Z 1
1 px
= p (x) (px ) e i ~ x dpx dx (7.131)
2 ~ 1 1
Recalling that Z 1
1
(x) = p (px ) eipx x=~ dpx ; (7.132)
2 ~ 1
we have Z 1
1 px
(x) = p (px ) e i ~ x dpx (7.133)
2 ~ 1
The wave function must be normalized at all time. Thus
Z 1
2
j (x)j dx = 1
1
Z 1 Z 1 Z 1
1 p0x
ipx x=~
) (px ) e dpx (p0x ) e i ~ x dp0x dx = 1
2 ~ 1 1 1
Z 1 Z 1 Z 1
1 0
) (px ) (p0x ) ei(px px )x=~ dx dp0x dpx
2 ~ 1 1 1
Z 1 Z 1 Z 1
0 0 0
= (px ) [ (px ) 2 ~ (px px ) dpx ] dpx = (px ) (px ) dpx
1 1 1
Z 1 Z 1
2 2
j (x)j dx = j (px )j dpx = 1 (7.134)
1 1
This result is known as Parseval’s theorem. It states that if a function is nor-

malized to 1, so is its Fourier transform.
7.8. THE WAVE FUNCTION AND THE MOMENTUM SPACE 179
We recall that the momentum expectation value is given by

Z 1
@ (x)
h^
px i = (x) i~ dx: (7.135)
1 @x
so that using
Z 1
1
(x) = p (px ) eipx x=~ dpx ; (7.136)
2 ~ 1
we may write
Z 1 Z 1
1 @
px i = p
h^ (x) i~ (px ) eipx x=~ dpx dx
2 ~ 1 @x 1
Z 1 Z 1
1 @ ipx x=~
=p (x) i~ (px ) e dpx dx
2 ~ 1 1 @x
Z 1 Z 1
1
=p (x) (px ) px eipx x=~ dpx dx
2 ~ 1 1
Z 1 Z 1
1
px i = p
) h^ (px ) px (x) eipx x=~ dx dpx : (7.137)
2 ~ 1 1
Noting that
Z 1 Z 1
1 i p~x x 1 px
(px ) = p e (x) dx ) (px ) = p ei ~ x
(x) dx
2 ~ 1 2 ~ 1
we can write Z 1
1
px i = p
h^ (px ) px (px ) dpx : (7.138)
2 ~ 1
As we have already shown, note that

Z 1
2
j (px )j dpx = 1 (7.139)
1
and Z 1
1
px i = p
h^ (px ) px (px ) dpx : (7.140)
2 ~ 1
From these results one can make the following conclusion remarks:
(a) (px ) is the wave function in momentum space
(b) The probability of …nding the particle having a momentum in the interval
px and px + dpx is given by
2
P (px ) dpx = j (px )j dpx (7.141)
(c) The expectation values for the position, in the momentum space, can be
expressed as
Z 1
@
h^
xi = dpx (px ) i~ (px )
1 @px
D E Z 1 @
) F^ (^
x) = dpx (px ) F^ i~ (px ) : (7.142)
1 @px
which means in the momentum space the operator for position is
@
x
^ = i~ : (7.143)
@px
HW: Show that the position operator in the momentum space is given by
@
x
^ = i~ : (7.144)
@px
Example 5 Consider a particle whose normalized wave function is

p
2 xe x x > 0
(x) = (7.145)
0 x<0
2
(a) For what value of the x does P (x) = j (x; t)j peak?
(b) Calculate hxi and x2 :
(c) What is the probability that the particle is found between x = 0 and x =
1= ?
(d) Calculate px i and p^2x :

(px ) and use this to calculate h^
(e) Show that the uncertainty principle is satis…ed for this particle.
Solution:
(a) For the maximum or minimum values, the probability density

2 3 2 2 x
P (x) = j (x)j = 4 x e (7.146)
satis…es the condition

dP (x) d 3 2 2 x
=0) 4 x e = 0 ) 2x 2 x2 e 2 x
=0
dx dx
1
) x = 0; x = (7.147)
Since for x = 0, P (x) = 0 and P (x) = 0, the peak must be x = 1

:
(b) Recalling that the expectation value for F^ (x) is given by

D E Z 1
F^ (x) = (x; t) F (x) (x; t) : (7.148)
1
we may write Z 1
2
hxn i = xn j (x)j dx (7.149)
1
so that using the given wave function, one can express
Z 1
n 3
hx i = 4 xn+2 e 2 x dx (7.150)
0
for n = 1 and 2, we …nd

3 2 3
hxi = ; hxi = 2 (7.151)
2
(c) The probability that the particle is found between x = 0 and x = 1= is

determined from
Z 1= Z 1= Z 1=
2
P (x) dx = j (x; t)j dx = 4 3 x2 e 2 x dx (7.152)
0 0 0
Using integration by part

Z Z
udv = uv vdu (7.153)
we may write
Z Z
xe 2 x
1 xe 2 x
e 2 x
xe 2 x dx = + e 2 x
dx = 2 (7.154)
2 2 2 (2 )
and
Z Z
x2 e 2 x
1
x2 e 2 x
dx = + xe 2 x
dx
2
" # 1=
x2 e 2 x
1 xe 2 x
e 2 x
= + 2 (7.155)
2 2 (2 ) 0
so that
Z 1= Z 1=
3
P (x) dx = 4 x2 e 2 x
dx
0 0
" " ##1= Z 1=
2 x x2 1 x 1
=e + 2 ) P (x) dx = 0:32
2 2 (2 ) 0
0
(7.156)
(d) We recall that Z 1

1 p
e i ~ x (x; 0) dx:
(p) = p (7.157)
2 ~ 1
so that for the given wave function, we can write
p Z 1 p Z 1
2 ip 2 @ ip
(p) = p xe ( ~ + )x dx = p e ( ~ + )x dx
2 ~ 0 2 ~@ 0
p " # r
2 @ 1 4 3 1
= p ip
) (p) = 2 (7.158)
2 ~@ ~ +
2 ~ ip
+ ~
Then the expectation value for the momentum, in the momentum space,
given by Z 1
2
hpi = p j (p)j dp; (7.159)
1
becomes Z 1
4 3 pdp
hpi = 2 = 0: (7.160)
2 ~ 1 p2 2
~2 +
Similarly
Z 1 Z 1 2
2 8 3 p2
p2 = p2 j (p)j dp = p2 + 2
dp (7.161)
0 2 ~ 0 ~2
Introducing the transformation of variable de…ned by
p = ~ tan ( ) ) dp = ~ sec2 ( ) d (7.162)
we …nd Z
3 2 =2
8 ~
p2 = sin2 ( ) d = 2 2
~ : (7.163)
0
(e) The uncertainties for the momentum and position can be expressed as
q q
2 2
p = hp2 i hpi ; x = hx2 i hxi (7.164)
Using the results above we …nd
s p
2
3 2 3 3 3 3
hxi = ; hxi = 2 ) x= 2
= (7.165)
2 2 2
and
hpi = 0; p2 = 2 2
~ ) p= ~ (7.166)
so that the uncertainty relation becomes
p p
3 3 ~
p x= ~= ~> : (7.167)
2 2 2
Example 6 The classical limit: Consider a particle of mass m in a potential
described by the function U (x) :
(a) Derive the time evolution of the position operator x and momentum op-
erator p^ for the case where these operators do not explicitly depend on
time:
(b) Combine the two results to show that
d2 dU (x)
m hxi = (7.168)
dt2 dx
(c) For the classical limit where potential is a slowly varying function and the
uncertainty becomes negligibly small,
x=x hxi << 1;
show that we obtain the classical equation of motion (Newton’s second
law)
d2 dU (x) dU (hxi) d2
m hxi = ' ) m 2 hxi ' F (hxi) (7.169)
dt2 dx d hxi dt
Solution: Consider an operator A^ representing an observable. The average

value of a measurement of this observable is given by the expectation
value D E Z 1
A^ = (x; t) A^ (x; t) dx: (7.170)
1
We recall the expectation value for an observable represented by an oper-
ator, in the Haisenberg picture, is given by
* +
d D Ê i Dh ^ ^ iE @ A^
A = A; H + : (7.171)
dt ~ @t
For this equation we have seen that if the operator has no explicit time
dependence, it reduces to
d D Ê i Dh ^ ^ iE
A = A; H ; (7.172)
dt ~
and also if the operator commutes with the Hamiltonian operator,
d D Ê D E
A = 0 ) A^ = Constant. (7.173)
dt
(a) Using the Hamiltonian operator

2
^ = p^x + U (x)
H (7.174)
2m
and the equation
d D Ê i Dh ^ ^ iE
A = A; H (7.175)
dt ~
one can write
d i p^2x i p^2 i
hxi = x; + U (x) = x; x h[x; U (x)]i
dt ~ 2m ~ 2m ~
d i i i
) hxi = x; p^2x h[x; U (x)]i = x; p^2x ;
(7.176)
dt 2m~ ~ 2m~
where we used
[x; U (x)] = 0: (7.177)
h i h i h i
^ B
A; ^ C^ = B
^ A;^ C^ + A; ^ C^
^ B (7.178)
we have
x; p^2x = p^x [x; p^x ] + [x; p^x ] p^x = 2i~^
px : (7.179)
so that
d i d 1 2
hxi = h2i~^
px i ) hxi = p^ : (7.180)
dt 2m~ dt m x
For the momentum operator
d i p^2x i p^2 i
h^
px i = p^x ; + U (x) = p^x ; x h[^
px ; U (x)]i
dt ~ 2m ~ 2m ~
d i
) h^
px i = h[^
px ; U (x)]i (7.181)
dt ~
Using the momentum operator, we may write
d d d
p^x = i~ ) [^
px ; U (x)] = i~ U (x) U (x)
dx dx dx
so that applying the relation

Z 1
hf (^
px )i = (x) f (^
px ) (x) dx: (7.182)
1
one can write for the expectation value

Z 1
d d
h[^
px ; U (x)]i = i~ (x) U (x) U (x) (x) dx
1 dx dx
Z 1 Z 1
d d
= i~ (x) [U (x) (x)] dx + i~ (x) U (x) (x) dx
1 dx 1 dx
Z 1 Z 1
d dU (x)
= i~ (x) U (x) (x) dx i~ (x) (x) dx
1 dx 1 dx
Z 1
d
+i~ (x) U (x) (x) dx
1 dx
Z 1
dU (x) dU (x)
) h[^px ; U (x)]i = i~ (x) (x) dx = i~
1 dx dx
(7.183)
There follows that

d i i dU (x) dU (x)
h^
px i = h[^
px ; U (x)]i = i~ = (7.184)
dt ~ ~ dx dx
(b) Now combining the results we obtained

d d dU (x)
m h^
xi = h^
px i ; h^pi = (7.185)
dt dt dx
we …nd
d2 d d2 dU (x)
m 2
hxi = h^
pi ) m 2 hxi = : (7.186)
dt dt dt dx
(c) We recall from classical mechanics the force is related to the potential energy
by
dU (x)
F (x) = (7.187)
dx
Let’s expand the force F (x) in Taylor series about the average value for
the measurement of the position particle, hxi ; which is the most probable
position of the particle
2
dF (x) x hxi d2 F (x)
F (x) = F (hxi) + (x hxi) +
dx x=hxi 2! dx2 x=hxi
3 3
x hxi d F (x)
+ :::: (7.188)
3! dx3 x=hxi
when the uncertainty in the measurement is negligible
x hxi << 1 (7.189)
we may approximate
dF (x)
F (x) ' F (hxi) + (x hxi)
dx x=hxi
2
dU (hxi) d U (hxi)
) F (x) ' (x hxi) (7.190)
d hxi d2 hxi
If we are strictly considering classical case
x = hxi (7.191)
we have
dU (hxi)
F (hxi) ' (7.192)
d hxi
one easily get NEWTON’S SECOND LAW!!!
d2
F (hxi) = m hxi (7.193)
dt2
Chapter 8
Classic 1-D quantum

problems
8.1 Time independent Schrödinger equation

Consider a particle with mass m con…ned to move in positive x-direction under
the in‡uence of a potential, V (x): We shall consider the Schrödinger equation
that describes this particle’s wave function when the potential is independent
of time. To this end, we may write
@ ~2 @ 2
i~ (x; t) = + V (x) (x; t) (8.1)
@t 2m @x2
as
@ ^ (x; t)
i~ (x; t) = H (8.2)
@t
where
^ = ~2 @ 2
H + V (x); (8.3)
2m @x2
For the case V (x) is independent of time, we may use separation of variable and
write the wave function as
(x; t) = T (t) u (x) (8.4)
so that we can write
@ dT (t)
i~ (x; t) = i~u (x) (8.5)
@t dt
and
^ (x; t) = T (t) ~2 d2 u (x)
H + V (x)u (x) : (8.6)
2m dx2
Substituting Eqs. (8.5) and (8.6) into Eq. (8.2), we have
dT (t) ~2 d2 u (x)
i~u (x) = T (t) + V (x)u (x) (8.7)
dt 2m dx2
187
188 CHAPTER 8. CLASSIC 1-D QUANTUM PROBLEMS
and dividing both sides by T (t) u (x)
1 dT (t) 1 ~2 d2 u (x)
i~ = + V (x)u (x) : (8.8)
T (t) dt u (x) 2m dx2
Since both the left and right sides of Eq. (8.8) depends on two independent
variables, t and x, respectively, each side must be equal to a constant. We call
this constant E
1 dT (t)
i~ = E; (8.9)
T (t) dt
1 ~2 d2 u (x)
+ V (x)u (x) = E: (8.10)
u (x) 2m dx2
The solution of Eq. (8.9) is given by
dT iE iE
= dt ) T (t) = Ce ~ t : (8.11)
T ~
We may rewrite Eq. (8.10) as
~2 d2 u (x)
+ V (x)u (x) = Eu (x) (8.12)
2m dx2
or
^ (x) = Eu (x)
Hu (8.13)
Eq. (8.13) is the time-independent Schrödinger equation where H ^ is the Hamil-
tonian operator given by Eq. (8.3). According to Eq. (8.13) when the Hamil-
tonian operator acts on the function u (x) it gives the function itself multiplied
by a constant factor E. We already know that this kind of equation is known
as the eigenvalue equation. Since the Hamiltonian operator, H; ^ is just the sum
^
of kinetic energy operator, K
2
^ = p^x = ~2 d2
K (8.14)
2m 2m dx2
and the potential energy V (x), Eq. (8.13) is known as the energy eigenvalue
equation where u (x) is the energy eigenfunction and E is the corresponding
energy eigenvalue. Eigenvalues can be discrete or continuum.
We have obtained the time dependent part T (t) and the space dependent
part u (x) ; which we found to be the energy eigenfunction, we can write the
wave function, generally, as
X Z
iE iE
t
(x; t) = CE uE (x) e ~ + dEC (E) uE (x) e ~ t ; (8.15)
E
where the …rst term is for a discrete and the second term for continuum eigen-
values.
8.2. THE EXPANSION POSTULATE AND ITS PHYSICAL INTERPRETATION189
8.2 The Expansion postulate and its physical in-

terpretation
In theoretical physics I we were introduced that a well behaved …nite function
in the interval ( 1; 1) can be expressed in terms of a linear superposition of
an orthonormal set of functions. Therefore, the wave function (x) which is
well behaved and …nite in the interval ( 1; 1) can be expressed as a linear
superposition of an orthonormal set of the energy eigen functions, un (x), as
1
X
(x) = an un (x) ; (8.16)
n=0
where the expansion coe¢ cients an are determined from the orthonormality
condition of the energy eigen functions. Multiplying both sides by um (x) dx
and integrating with respect to x, one can write
Z 1 X1 Z 1
um (x) (x) dx = an un (x) um (x) dx: (8.17)
1 n=0 1
For an orthonormal set of functions, un (x) ; (like the energy eigen functions),
we have Z 1
un (x) um (x) dx = nm (8.18)
1
so that
Z 1 1
X Z 1
um (x) (x) dx = an nm ) am = um (x) (x) dx: (8.19)
1 n=0 1
When we include the time factor each eigen function has energy dependence En
and the wave function becomes
1
X iEn t
(x; t) = an un (x) e ; (8.20)
n=0
~
where the expansion coe¢ cients are still given by Eq. (8.19)
The square of the magnitude of the expansion coe¢ cient: it gives the proba-
bility of a measurement gives an energy value En :The sum of these probabilities
must be equal to one provided the wave function is normalized.
Z 1 X1 X 1 i(Em En )t Z 1
2
(x; t) (x; t) dx = jam j e um (x) un (x) dx
1 m=0 n=0
~ 1
X1 X 1 i(Em En )t Z 1 X1
2 2
= jam j e nm ) (x; t) (x; t) dx = jan j (8.21)
m=0 n=0
~ 1 n=0
For a normalized wave function

Z 1
(x; t) (x; t) dx = 1 (8.22)
1
and we …nd
1
X 1
X 2
pn = jan j = 1 (8.23)
n=0 n=0
Expansion coe¢ cient and energy expectation values: We can generalize, from
our discussion of expectation value of momentum in position space, the expec-
tation value of an observable described by an operator A^ in the position space
is given by
D E Z 1
A^ = (x; t) A^ (x; t) dx: (8.24)
1
For the energy operator (Hamiltonian operator), using Eq. (8.20) and its com-
plex conjugate
X1 iEm t
(x; t) = am um (x) e : (8.25)
m=0
~
we can then write
D E Z 1 X 1 iEm t X1 iEn t
H^ = am um (x) e ^
H an un (x) e dx; (8.26)
1 m=0 ~ n=0
~
which can be put in the form

D E X1 X
1 i(Em En )t Z 1
^ 2 ^ n (x) dx:
H = jam j e um (x) Hu (8.27)
m=0 n=0
~ 1
We recall the energy eigenvalue equation

^ n (x) = En un (x)
Hu (8.28)
and the above equation becomes

D E X 1
1 X i(Em En )t Z 1
^ = 2
H jam j En e um (x) un (x) dx: (8.29)
m=0 n=0
~ 1
using the orthonormality condition for the energy eigen functions

Z 1
um (x) un (x) dx = nm (8.30)
1
we …nd
D E X1 X
1 i(Em En )t 1
X
^ = 2 2
H jam j En e nm = jan j En : (8.31)
m=0 n=0
~ n=0
The result in equation in Eq. (8.31) means that the average energy of a
system is equal to
D E X1 1
X
^ 2
Eav = H = jan j En = pn En ; (8.32)
n=0 n=0
8.3. PARTICLE IN ONE DIMENSIONAL BOX 191
where
2
pn = jan j (8.33)
is the probability that a measurement in energy yields, En : It is important to
note that a quantum measurement projects the state into an eigenstate of the
observable that is being measured.
8.3 Particle in one dimensional box

Example 1 Consider a particle of mass, m; in a potential de…ned by
8
< 1 x<0
V (x) = 0 0<x<a (8.34)
:
1 a<x
(a) Find the energy eigenvalues and eigenfunctions
(b) Verify that if the energy eigenfunctions are orthogonal.
(c) Are the energy eigenfunctions orthonormal If not normalize it.
(d) For the ground state …nd the energy, the expectation value for hpx i ; p2x ,
and the uncertainty px :
(e) Suppose the width of the box is 1cm, roughly, what value of n corresponds
to the state of 0:01ev if the particle is an electron. How cold the electron
must be to be in this state (i.e. …nd T )
(f ) Calculate the density of states in the vicinity of 0:01eV . What is the number
of states within the interval of 0:0001eV about the energy of 0:01eV
Hint: Density of state is given by dn=dE:
(g) By plotting the energy eigenfunctions for the ground state and the …rst few
excited states and observing the symmetry determine the eigenfunction
for a particle of mass, m; in a potential V (x) de…ned by
8
< 1 x < a=2
V (x) = 0 a=2 < x < a=2 (8.35)
:
1 a=2 < x
Solution:
(a) The energy eigenvalue equation in the region, 0 < x < a; can be expressed
as
~2 d2 u (x)
= Eu (x) ; (8.36)
2m dx2
which can be expressed as

d2 u (x)
+ q 2 u (x) = 0; (8.37)
dx2
where
2mE
q2 = : (8.38)
~2
The solution to Eq. (8.38) is given by
u (x) = A cos (qx) + B sin (qx) : (8.39)
Since the particle can not exist outside the box the eigen function must
vanish at the boundaries,
n
u (0) = 0 ) A = 0; u (a) = 0 ) B sin (qa) = 0 ) q = ; n = 1; 2; 3:::
a
(8.40)
Therefore the eigenfunction and the corresponding eigen values are dis-
crete and are given by
2 2 2
n ~ n
un (x) = Bn sin x ; En = : (8.41)
a 2ma2
(b) If the energy eigenfunctions are orthogonal it must satisfy the condition
(From Theoretical Physics 1 )
Z 1
const n = m
un (x) um (x) dx = (8.42)
1 0 n 6= m
Using the eigenfunction in part (a) we have

Z 1 Z a
2 n m
un (x) um (x) dx = Bn sin x sin x dx (8.43)
1 0 a a
and using
n m 1 (n m) (n + m)
sin x sin x = cos x cos x
a a 2 a a
(8.44)
we …nd
Z 1 Z
B2 a (n m) (n + m)
un (x) um (x) dx = n cos x cos x dx
1 2 0 a a
Z Ra
Bn2 a (n m) Bn2 0
dx n = m
= cos x dx = (8.45)
2 0 a 2 0 n 6= m
Z 1 ( 2
aBn
) un (x) um (x) dx = 2 n=m (8.46)
1 0 n 6= m
Therefore the eigenfunctions are orthonormal

(c) Although the eigen functions are orthogonal we can not say it is orthonor-
mal. For the functions to be orthonormal the orthonormality condition
Z 1
un (x) um (x) dx = nm (8.47)
1
must be satis…ed. Using the result in part (b), the orthonormalized eigen
functions can be written as
r
2 n
un (x) = sin x : (8.48)
a a
(d) The ground state energy is the minimum energy which is given by the
minimum quantum number, n = 1
2 2
~
E1 = : (8.49)
2ma2
The expectation values for hpx i which is given by
Z 1
@
hpx i = (x; t) i~ (x; t) dx; (8.50)
1 @x
can be expressed for the ground state as in terms of the energy eigen
functions as
Z Z !
1 a
@ 2i~ @ sin a x
hpx i = u1 (x) i~ u1 (x) dx = sin x dx
1 @x a 0 a @x
Z a
2i~
= sin x cos x dx ) hpx i = 0: (8.51)
a a 0 a a
For p2x ; we can use the energy eigenvalue. We know that in the region
0 < x < a; since V (x) = 0
2 D E p^2x p^2x n 2 2 ~2 2 2
^ = p^x ) H
H ^ = = En ) = ) p
^2
x =
~
:
2m 2m 2m 2ma2 a2
(8.52)
Then the uncertainties in momentum
q
2 ~
p = hp2 i hpi ) p= (8.53)
a
(e) For a width

2
a = 10 m (8.54)
and energy
19
E = 0:01ev = 0:01 1:6 10 J (8.55)
solving for n from Eq. (8.41), we …nd

r
2ma2 En
n= 2 ~2
= 1:63 104 :
For a free particle in one dimensional box, the thermal energy equal to
the kinetic energy (total energy) is given by
1
E= KT; (8.56)
2
where K = 8:62 10 5 ev=K is the Boltzman constant. Then temperature
becomes
2E 2 0:01ev
T = = = 232K: (8.57)
K 8:62 10 5 ev=K
dn
(f ) The density of state is given by dE : Using the energy
2 2
~ 2
E (n) = n ; (8.58)
2ma2
we may write
2 2
~ n dn ma2 n n
dE = dn ) = = 2 ~ 2 n2 = : (8.59)
ma2 dE 2 ~2 n
2 2ma2
2E
Numerically
dn n 1:63 104 1
= = = 0:82 106 : (8.60)
dE 2E 2 10 2 ev ev
Therefore, the number of states, n in an energy interval E = 0:0001eV
is
E+Z E
dn 1
n= dE = 0:82 106 E = 82 (8.61)
dE ev
E
states.
(g) The plots for the eigen functions are given belowFor a particle in a one
dimensional box with boundaries at x = a=2 and x = a=2
8
< 1 x < a=2
V (x) = 0 a=2 < x < a=2 (8.62)
:
1 a=2 < x
the eigen functions can be determined by shifting the graphs to the left
by 0.5a. That leads to
n a
un (x) = Bn sin x+
h a 2
n x n n x n i
= Bn sin cos + cos sin (8.63)
a 2 a 2
Bn sin na x n = even
) un (x) = (8.64)
Bn cos na x n = odd
where we have included the negative signs into the normalization constant.
Figure 8.1: The energy eigen functions: n = 1 (Red), n = 2 (green), n = 3

(blue), and n = 4 (black).
Example 2 Suppose the particle in the one-dimensional box considered in the

example above has a wave function given by
A(x=a) 0 < x < a=2

(x) = (8.65)
A(1 x=a) a=2 < x < a
p
where A = 12=a is the normalization constant. Calculate the probability
that a measurement of the energy for this particle yields the value, En :
Solution: We recall the wave function in terms of the energy eigen functions
can be expressed as
1
X iEn t
(x; t) = an un (x) e ; (8.66)
n=0
~
where the expansion coe¢ cients are determined using

Z 1
an = un (x) (x) dx: (8.67)
1
For a particle in a box described by the wave function above, we may write
Z a=2 Z a
an = un (x) A(x=a)dx + un (x) A(1 x=a)dx: (8.68)
0 a=2
Using the result for the eigen function of a particle in a box con…ned in
the region, 0 < x < a
r
2 n
un (x) = sin x : (8.69)
a a
we …nd
r Z a=2
r Z a
2 n x 2 n x
an = A sin x dx+ A sin x (1 )dx (8.70)
a 0 a a a a=2 a a
Introducing transformation of variable de…ned by

u x
1 = (8.71)
a a
we have
a a
dx = du; x = ) u = ;x = a ) u = 0
2 2
n n n n n
sin x = sin n u = cos (n ) sin u = ( 1) sin u
a a a a
(8.72)
so that one can express the integral

Z a Z 0
n x n n u
sin x (1 )dx = ( 1) sin u du
a=2 a a a=2 a a
Z a=2
n n u
= ( 1) sin u du
0 a a
Z a Z a=2
n x n n x
) sin x (1 )dx = ( 1) sin x dx (8.73)
a=2 a a 0 a a
where we take into account the fact that u is a dummy variable in the last
step. The substituting this into the equation for an ; we …nd,
r Z a=2
2 n n x
an = A (1 ( 1) ) sin x dx: (8.74)
a 0 a a
We may put this equation in the form

r Z a=2
2 n a n n x n x
an = A (1 ( 1) ) 2 2 sin x d
a n 0 a a a
r Z n =2
2 n a
) an = A (1 ( 1) ) 2 2 sin (v) vdv: (8.75)
a n 0
Using integration by parts, one can rewrite

r ( Z n =2 )
2 n a n =2
an = A (1 ( 1) ) 2 2 [ cos (v) v]0 + cos (v) dv
a n 0
r
2 n a n =2
= A (1 ( 1) ) 2 2 fsin (v) cos (v) vg0
a n
r
2 n a n n n n o
) an = A (1 ( 1) ) 2 2 sin cos (8.76)
a n 2 2 2
there follows that
8
>
< 0
p
n = even
96
an = 2 n2 n = 1; 5; 9::: (8.77)
>
:
p
96
2 n2 n = 3; 7; 11::
p
where we substituted, A = 12=a. The the probability that a measure-
ment results in energy value En is given by
2 0 n = even
pn = jan j = 96 (8.78)
4 n4 n = odd
Example 3 At t = 0 a particle is known to be localized in the left half of a

one-dimensional box with sides at x = a=2, with the wave function
( q
2 a
(x; t = 0) = a 2 <x<0 (8.79)
0 0 < x < a2
(a) Will the particle remain localized at a later time, t?
(b) Calculate the probability that an energy measurement yields the ground
state energy and also the energy of the …rst excited state.
Solution:
(a) The particle will not remain localized. Its motion is governed by the Hamil-
tonian
2
H^ = p^x (8.80)
2m
inside the region a2 < x < a2 at a letter time since it is free to move
inside the box. However, at time t = 0, the particle is localized in the left
half region of the box and initial the initial wave function is
( q
2 a
(x; 0) = a 2 <x<0 (8.81)
0 0 < x < a2
Thus at a later time, t, the wave function

1
X iEn t
(x; t) = an un (x) e : (8.82)
n=0
~
In example one we have determined for a particle in a one-dimensional box
where the boundaries of the box shifted to the left by a=2 (i.e. boundaries
at x = a=2) the energy eigenvalue does not change
2 2 2
~ n
; En = (8.83)
2ma2
but the eigen function would change. We found these eigenfunction to be
n x
Bn sin a n = even
un (x) = n x (8.84)
Bn cos a n = odd
which can be normalizing,
8 q
< 2
sin n x
n = even
un (x) = qa a
(8.85)
: 2 n x
a cos a n = odd
At a later time, t; the wave function which can be expressed in terms of
these eigen functions and eigenvalues
1
X iEn t
(x; t) = an un (x) e : (8.86)
n=0
~
must reduce to the wave function at the initial time t = 0. Thus one must
have ( q
X1 2 a
(x; 0) = an un (x) = a 2 <x<0 : (8.87)
n=0 0 0 < x < a2
where the expansion coe¢ cients an can be determined using
Z 1
am = um (x) (x; 0) dx: (8.88)
1
(b) We …rst calculate the expansion coe¢ cients

Z 0 r
2
an = un (x) dx (8.89)
a
2
a
which is found to be
( 2
R0 n x
a a sin a dx n = even
an = 2
R02 n x
(8.90)
a a cos a dx n = odd
2
8 0
>
> 2 cos( a )
n x
8
>
< a n n = even < 0 n = even
a a
2
= 0
2 ) an = n n = 1; 5; 9:::
>
> 2 sin( a )
n x : 2
>
: a n n = odd n n = 3; 7; 11::
a a
2
Therefore, the wave function becomes

1
X iEn t
(x; t) = an un (x) e : (8.91)
n=1
~
where an is given by Eq. (8.90). Then the probability that an energy

measurement yields the energy eigenvalue, En , given by
2 0 n = even
pn = jan j = 4 (8.92)
n2 2 n = odd
gives for the ground state energy, E1 ;
2 4
p1 = ja1 j = 2
' 0:41; (8.93)
and for the …rst excited state (n = 3), E2 ;
2 4
p3 = ja3 j = 2
' 0:05: (8.94)
9
HW:
(a) Noting that

up (x) = hxj pi (8.95)
show that Z 1
up0 (x) up (x) dx = (p p0 ) (8.96)
1
(b) For a free particle, starting from

Z 1
(x) = (p) up (x) dp; (8.97)
1
and applying the result in part (a) show that the momentum eigen func-
tions can be expressed in terms of the wavefunction as
Z 1
(p) = up0 (x) (x) dx; (8.98)
1
Example 4 A particle is in the ground state of a box with sides at x = 0 and

x = a. Suddenly the walls of the box are moved to 1, so that the particle
is free. What is the probability that the particle has momentum in the
range (p; p + dp)? Since a free particle of momentum p has energy p2 =2m;
which need not equal the ground-state energy, energy is not conserved.
How is this possible?
Solution: Initially the particle was in a box in its ground state. That means
at t = 0, the wave function of the particle is given by the eigen function
of a particle in a box
r
2 n
un (x) = sin x : (8.99)
a a
For n = 1, which is
( q
2 x
sin 0<x<a
(x) = a a (8.100)
0 x < 0 and x > a
However, at a later time since the particle is set free the wave function
must be expressed as
Z 1
(x) = (p) up (x) dp; (8.101)
1
where the square of the magnitude of the expansion coe¢ cient (p) ;
Z 1
(p) = up0 (x) (x) dx; (8.102)
1
is the probability that the particle has a momentum p: Therefore using

the given initial wave function and the momentum eigen function
1 p
up (x) = p ei ~ x (8.103)
2 ~
for a free particle, we may write
Z a r r Z a x x
1 p
i~ x 2 x 1 p ei a e ia
(p) = p e sin dx = e i~x dx
0 2 ~ a a ~a 0 2i
Z a p p
! r " p p
#a
ei( a ~ )x e i( a + ~ )x 1 ei( a ~ )x e i( a + ~ )x
= p dx = +
0 2i ~a ~a 2 a ~p 2 a + ~p
0
r " p p
#
i( a ~ ) a i( a + ~ )a
1 e 1 e 1
) (p) = p + p (8.104)
~a 2 a ~ 2 a+~

p
i 2~ 2 =a cos (pa=2~)
(p) = e p (8.105)
~a a 2 p 2
~
Therefore, the probability that the particle has momentum in the range
(p; p + dp) is given by
2 4 cos2 (pa=2~)
j (p)j dp = h i2 dp (8.106)
~a3 2 p 2
a ~
8.4. THE STEP POTENTIAL 201
8.4 The step potential

We consider a particle with mass m and total energy E which is free to move in
a region x < 0: However, in the region x > 0 it subject to a constant potential
V0 : Such potential is described by
0 x<0
V (x) = (8.107)
V0 x>0
and it is known as the step potential. We assume that the particle is coming
from the left as shown in the …gure below.The Shröudinger equation in the
region x < 0 can be written as

~2 d2 u (x) d2 u (x) 2mE
= Eu (x) ) + 2 u (x) = 0
2m dx2 dx2 ~
d2 u (x)
) + k 2 u (x) = 0; (8.108)
dx2
where
2mE
k2 = : (8.109)
~2
In the region x > 0
~2 d2 u (x) d2 u (x) 2m (E V0 )
+ V0 u (x) = Eu (x) ) + u (x) = 0
2m dx2 dx2 ~2
d2 u (x)
) + q 2 u (x) = 0; (8.110)
dx2
where
2m (E V0 )
q2 = : (8.111)
~2
The general solutions of Eqs (8.108) and (8.110) are given by
Aeikx + Re ikx
; x<0
u (x) = (8.112)
T eiqx ; x>0
where we dropped the De iqx term in the region x > 0 since there is nothing
that causes the particle to reverse its direction. However, in the region x < 0,
that particle could get re‡ected because of the potential it encountered at x = 0

and we keep the term Re ikx :Imposing the condition that the wave function
and its derivative must be continuous everywhere including at, x = 0, where
the potential abruptly changes, we …nd
q
A + R = T; ik (A R) = iqT ) A + R = T; A R= T (8.113)
k
In terms of the incident wave amplitude A; we may write
q k 2k
R= A; T = A (8.114)
q+k q+k
The incident, re‡ected, and transmitted ‡ux : We recall that the probability
current density, J (x; t) ; which is given by
~ @ @
J (x; t) = (x; t) (x; t) (x; t) (x; t) ; (8.115)
2mi @x @x
tells us the ‡ux of particles incident, re‡ected or transmitted at a given position,
x and at time, t. Using this relation and the results obtained above we may
write the net ‡ux of particle incident at x = 0 as
~ @ @
Jnet in (0; t) = u (x) u (x) u (x) u (x) ; (8.116)
2mi @x @x x=0
using the wave function for x < 0; we have

@ ikx
u (x) u (x) = ik Ae + Reikx Aeikx Re ikx
@x
@ 2 2
) u (x) u (x) = ik (A + R ) (A R) = ik jAj jRj (8.117)
@x x=0
and
@
u (x) u (x) = ik Aeikx + Re ikx
A e ikx
R eikx
@x
@ 2 2
) u (x) u (x) = ik jAj jRj (8.118)
@x x=0
so that
~ h 2 2 2 2
i
Jnet in (0; t) = ik jAj jRj + ik jAj jRj ; (8.119)
2mi
~k 2 2
) Jnet in (0; t) = jAj jRj : (8.120)
m
The net ‡ux of particle transmitted into the region, x > 0
~ @ @
Jnet tr (0; t) = u (x) u (x) u (x) u (x) ;
2mi @x @x x=0
using the wave function in the region x > 0, we have
@ iqx 2 @
u (x) u (x) = iqT e T eiqx = iq jT j ) u (x) u (x) = iqT 2
@x @x x=0
(8.121)
and
@
u (x) u (x) = iqT 2 (8.122)
@x x=0
so that
~q 2
Jtr (0; t) = T : (8.123)
m
Recalling that
@ @
P (x; t) = J (x; t) (8.124)
@t @x
when the wave function does not change with time
@ @
J (x; t) = P (x; t) = 0 ) J (x; t) = constant (8.125)
@x @t
which gives
~k 2 2 ~q 2
jAj jRj = jT j (8.126)
m m
From Eq. (8.126), we note that the incident ‡ux is
~k 2
jin = jAj (8.127)
m
the re‡ected ‡ux
~k 2
jre = jRj (8.128)
m
and the transmitted ‡ux
~q 2
jtr = jT j (8.129)
m
so that
~k 2 2 ~q 2
jAj jRj = jT j ) Jnet in (0; t) = Jnet tr (0; t)
m m
) jin + jre = jtr (8.130)
Using the results in Eq. (8.114) the re‡ected and transmitted ‡ux in terms of
the amplitude of the incident wave can be expressed as
2
~k q k 2
jre = jAj (8.131)
m q+k
and
2
~q 2k 2
jtr = jAj : (8.132)
m q+k
The probability that the particle gets re‡ected is given by the ratio of the
re‡ected ‡ux to the incident ‡ux
2
~k q k 2
jre m q+k jAj q k
2
= ~k 2 = (8.133)
jin jAj q+k
m
the probability that it gets transmitted

2
~q 2k 2
jtr m q+k jAj 4 jkqj
= ~k 2 = 2 (8.134)
jin jAj jq + kj
m
2 2
which shows that jRj and jT j represent the re‡ection and transmission prob-
ability, respectively
Classical and Quantum:
(a) Particle with energy, E < V0 : Classically, we know that when a particle
with energy E encounter a potential V0 , if E > V0 , it just slow down and
continues to move in the same direction. It will never change its direction
and be re‡ected. But quantum mechanics predicts that there is a good
chance determined by the probability in Eq. (8.133) which depends on q
(the relative di¤erence between the energy of the incident particle and the
potential). For E >> V0 ; we can make the approximation
2m (E V0 ) 2mE
q2 = = = k 2 ) q = k: (8.135)
~2 ~2
so that the re‡ection probability
2
2 q k
jRj = =0
q+k
which agrees with intuition. It tells us that at very high energies the
particle will never be re‡ected. The presence of the step is just causes a
small perturbation on the propagation of the wave (particle).
(b) Particle with energy, E < V0 : When the incident particle has energy less
than the potential energy, the expression in Eq. (8.111) becomes
2m (E V0 ) 2m jE V0 j 2m jE V0 j
q2 = ) q 02 = ) q 02 =
~2 ~2 ~2
(8.136)
which leads to
q0 = iq (8.137)
where
2m jE V0 j
q= : (8.138)
~2
Using the result in Eq. (8.137) and following the same justi…cation we
used in the previous case, the wave function Eq. (8.112) becomes
Aeikx + Re ikx
x<0
u (x) = (8.139)
T e qx x>0
Using the continuity of the wave function and its derivative at x = 0,

which leads to
q
A + R = T; ik (A R) = qT ) A + R = T; A R= T
ik
In terms of the incident wave amplitude A; we may write
iq k 2iq
R= A; T = A (8.140)
iq + k iq + k
The re‡ected ‡ux
~k 2 ~k iq k iq k 2 ~k 2
jre = jRj = jAj ) jre = jAj
m m iq + k iq + k m
and the transmitted ‡ux
~q 2 ~q 2iq 2iq 2
jtr = jT j = jAj
m m iq + k iq + k
~q 4q 2 2
) jtr = 2
jAj : (8.141)
m k q2
Then the probability of being re‡ected
jre
=1 (8.142)
jin
Thus as in classical mechanics, there is now total internal re‡ection. How-

ever, the probability that it gets transmitted
jtr q 4q 2
= : (8.143)
jin k k2 q2
does not vanish and a part of the wave penetrates into the forbidden
region. This penetration phenomenon again is characteristics of waves.
As we will see next this permits a "tunneling" though barriers that would
totally block particles in a classical description.
For those of you who took Theoretical Physics III (Electricity and Magnetism
I & II) I would like you to refer to Chapter 9 section 9.4 and 9. 11.
8.5 The potential barrier and quantum tunnelling

Example 5 The potential barrier and quantum tunnelling: Consider a particle
with a total energy E is incident on a one dimensional potential barrier
described by 8
< 0; x< a
V (x) = V0 ; a<x<a (8.144)
:
0; x>a
For a particle with energy, E, less than the potential barrier, E < V0 ;
(a) By solving the SE in the three region and providing convincing physical
justi…cation show that
8
< Aeikx + Re ikx x< a
u (x) = Ceqx + De qx a<x<a (8.145)
:
T eikx x>a
where r
2mE
k= : (8.146)
~2
and r
2m jE V0 j
q= : (8.147)
~2
(b) Show that the tunneling probability (the transmission probability though
the potential barrier) is
2 2
jtr jT j (2kq)
= 2 = 2 (8.148)
jin jAj 4 (k + q ) sinh2 (2qa) + (2kq)2
2 2
Solution:
(a) In the regions x < a and x > a since the potential is zero, one can write
can be written the Shröudinger equation as
~2 d2 u (x) d2 u (x) 2mE
2
= Eu (x) ) + 2 u (x) = 0
2m dx dx2 ~
d2 u (x)
) + k 2 u (x) = 0; (8.149)
dx2
where
2mE
k2 = : (8.150)
~2
In the region a<x<a
~2 d2 u (x) d2 u (x) 2m jE V0 j
2
+ V0 u (x) = Eu (x) ) u (x) = 0
2m dx dx2 ~2
d2 u (x)
) q 2 u (x) = 0; (8.151)
dx2
8.5. THE POTENTIAL BARRIER AND QUANTUM TUNNELLING 207
where
2m jE V0 j
q2 = : (8.152)
~2
The general solutions in the three regions can then be written as are given
by
8
< Aeikx + Re ikx ; x< a
u (x) = Ceqx + De qx a<x<a (8.153)
:
T eikx ; x>a
where we dropped the De iqx term in the region x > 0 since there is
nothing that causes the particle to reverse its course.
(b) Imposing the condition that the wave function and its derivative must be
continuous everywhere including at, x = a and x = a, we …nd
ika
Ae + Reika = Ce qa
+ Deqa
ika ika qa
ik Ae Re = q Ce Deqa
Ceqa + De qa
= T eika
q Ceqa De qa
= ikT eika (8.154)
From the …rst two equations, we have
ika ik
Ae + Reika = Ce qa
+ Deqa ; Ae ika
Reika = Ce qa
Deqa
q
(8.155)
so that one may express
ika ik
Ae + Reika + q Ae
ika
Reika
C=
2e qa
eqa ik ika ik
)C= 1+ Ae + 1 Reika (8.156)
2 q q
ika ik
Ae + Reika q Ae ika
Reika
D=
2eqa
qa
e ik ika ik
)D= 1 Ae + 1+ Reika : (8.157)
2 q q
Similarly from the second pair of equations, we …nd
ik ika
Ceqa + De qa
= T eika ; Ceqa De qa
= Te
q
qa
e ik eqa ik
)C= 1+ T eika ; D = 1 T eika (8.158)
2 q 2 q
There follows that

qa
e ik eqa ik ik
1+ T eika = 1+ Ae ika + 1 Reika
2 q 2 q q
2qa q ik
) Te R = Ae 2ika (8.159)
q + ik
and
eqa ik e qa
ik q + ik ika
1 T eika = 1 Ae ika
+ Re
2 q 2 q q ik
q + ik
) T e2qa R = Ae 2ika
(8.160)
q ik
Noting that
2qa q ik q + ik q + ik
Te R = Ae 2ika ) T e 2qa R = A e 2ika
q + ik q ik q ik
q + ik q ik q ik
T e2qa R = Ae 2ika ) T e2qa R = A e 2ika ;
q ik q + ik q + ik
(8.161)
upon subtracting these two equations, we have

q + ik 2qa q ik 2qa q + ik q ik
T e e =A e 2ika
q ik q + ik q ik q + ik
!
q2 k 2 + 2iqk e 2qa
q2 k2 2iqk e2qa
)T
q2 + k2
q2 k 2 + 2iqk q2 k2 2iqk 2ika
=A e
q2 + k2
!
k2 q2 e2qa e 2qa
+ 2ikq e2qa + e 2qa
)T
q + k2
2
q2 k 2 + 2iqk q2 k2 2iqk 2ika

=A e
q + k2
2
!
2 k2 q 2 sinh (2qa) + 4ikq cosh (2qa) 4iqk 2ika
)T =A e
q2 + k2 q2+ k2
which results in
2ika
2iqke
T = A: (8.162)
(k 2 q 2 ) sinh (2qa) + 2ikq cosh (2qa)
Substituting this expression into
q + ik 2qa q + ik 2ika
T e R=A e
q ik q ik
one …nds for the re‡ection amplitude
2qa 2ika q + ik
R = Te Ae
q ik
2iqke 2qa 2ika
= 1 e A
(k 2 q 2 ) sinh (2qa) + 2ikq cosh (2qa)
Using
2qa
e = cosh (2qa) sinh (2qa)
we …nd
2
(k iq) sinh (2qa) 2ika
R= e A
(k 2 2
q ) sinh (2qa) + 2ikq cosh (2qa)
The transmission probabilities becomes
2 2
jtr jT j (2qk)
= 2 = 2 2 (8.163)
jin jAj (k 2 q 2 ) sinh2 (2qa) + (2kq) cosh2 (2qa)
using the relation

cosh2 (2qa) = 1 + sinh2 (2qa) (8.164)
we may write
2 2
jT j (2qk)
2 = h i
2 2 2
jAj (k 2 q 2 ) + (2kq) sinh2 (2qa) + (2kq)
2 2
jT j (2kq)
) 2 = 2 (8.165)
jAj (k 2 + q 2 ) sinh2 (2qa) + (2kq)2
For the the re‡ection probability
2
jtr jRj
2
k2 + q2 sinh2 (2qa)
= 2 = 2 2 (8.166)
jin jAj (k 2 q 2 ) sinh2 (2qa) + (2kq) cosh2 (2qa)
2
jRj
2
k2 + q2 sinh2 (2qa)
) 2 = 2 (8.167)
jAj (k 2 + q 2 ) sinh2 (2qa) + (2kq)2
Note that
2 2
jRj jT j
2 + 2 =1 (8.168)
jAj jAj
as one should expect.

Alternative approach: Noting that thefour equations resulting from imposing

the boundary conditions
ika
Ae + Reika = Ce qa
+ Deqa ) Reika Ce qa
Deqa = Ae ika
ika
ik Ae Reika = q Ce qa
Deqa
) Rikeika Cqe qa
+ Dqeqa = Aike ika
Ceqa + De qa
= T eika ) Ceqa + De qa
T eika = 0
q Ceqa De qa
= ikT eika ) Cqeqa Dqe qa
T ikeika = 0 (8.169)
can be put in a matrix form as

2 32 3 3 2
eika e qa eqa 0 R Ae ika
6 ikeika qe qa
qeqa
0 76 C
7 6 Aike ika 7
6 7
7=66 7
4 0 e qa
e qa eika 5 4 D
5 4 0 5
qa
0 qe qe qa ikeika T 0
(8.170)
Applying Cramer’s rule from theoretical physics I, one can express the
solutions for R; C; D; and T in terms of the incident wave applitude A as
det jM1 j det jM2 j det jM3 j det jM4 j

R= ;C = ;D = ;T = (8.171)
det jM j det jM j det jM j det jM j
where
2 3
eika e qa eqa 0
6 ikeika qe qa qeqa 0 7
M = 6 7
ika 5 ;
4 0 eqa e qa e
0 qeqa qe qa ikeika
2 3
Ae ika e qa eqa 0
6 Aike ika qe qa qeqa 0 7
M1 = 6 7
ika 5 ;
4 0 eqa e qa e
0 qeqa qe qa ikeika
2 3
eika Ae ika eqa 0
6 ikeika Aike ika qeqa 0 7
M2 = 6 7
ika 5 ;
4 0 0 e qa e
0 0 qe qa ikeika
2 3
eika e qa Ae ika 0
6 ikeika qe qa Aike ika 0 7
M3 = 6 7
ika 5 ;
4 0 eqa 0 e
0 qeqa 0 ikeika
2 3
eika e qa eqa Ae ika
6 ikeika qe qa qeqa Aike ika 7
M4 = 6 7;
4 0 eqa e qa 0 5
0 qeqa qe qa 0
One can can also express the solutions as
2 3 2 3
R Ae ika
6 C 7 6 Aike ika 7
6 7 1 6 7
4 D 5=M 4 0 5 (8.172)
T 0
1
where M is the inverse of the matrix M . Using Mathematica,
one can write for the re‡ection and transmission amplitudes
2 2ika
3
e (k2 +q2 )(e4qa
1)
R
=4 k2 (e4qa 1)+2ikq(e4qa +1) q 2 (e4qa 1) A 5
2a(q ik)
T 4ikqe
k2 (e4qa 1)+2ikq(e4qa +1) q 2 (e4qa 1) A
Since we are interested in the refelected and transmitted ‡ux density,
2 2
2ika
jRj e k 2 + q 2 e4qa 1
2 =
jAj k 2 (e4qa 1) + 2ikq (e4qa + 1) q 2 (e4qa 1)
2 2 2qa 2
k2 + q e2qa e
=
[(k 2 q 2 ) (e2qa e 2qa )]2 2
+ 4 (kq) (e2qa + e 2qa )2
2
k2 + q2 sinh2 (2qa)
= 2 2
(k 2 q 2 ) sinh2 (2qa) + 4 (kq) cosh2 (2qa)
2
k2 + q2 sinh2 (2qa)
= h i
2 2 2
(k 2 q 2 ) + 4 (kq) sinh2 (2qa) + 4 (kq)
2
jRj
2
k2 + q2 sinh2 (2qa)
) 2 = 2 2 (8.173)
jAj (k 2 + q 2 ) sinh2 (2qa) + (2kq)
Similarily
2 2
jT j 4ikqe2a(q ik)
2 =
jAj k 2 (e4qa 1) + 2ikq (e4qa + 1) q 2 (e4qa 1)
2
(2kq)
=
[(k 2 q 2 ) (e2qa e 2qa )]2 2
+ 4 (kq) (e2qa + e 2qa )2
2 2
jT j (2kq)
) 2 = 2 2
(8.174)
jAj (k 2 + q2 ) sinh (2qa) + (2kq)2
which are the same as the result we obtained without using matrices.
8.6 The potential well and bound states

A potential well is de…ned by the function
8
< 0 x< a
V (x) = V0 a<x<a (8.175)
:
0 x>a
A particle traveling from left to right in such kind of potential, exhibit two
di¤erent properties when the energy of the particle is positive (E > 0) and
negative (E < 0). We will consider these two cases separately.
Positive energy (E>0): We shall …rst consider when the energy is positive
as shown in the …gure below
The Schrödinger equation in the region x < a and x > a can be written as
~2 d2 u (x) d2 u (x)
= Eu (x) ) + k 2 u (x) = 0; (8.176)
2m dx2 dx2
8.6. THE POTENTIAL WELL AND BOUND STATES 213
where
2mE
k2 = : (8.177)
~2
In the region a<x<a
~2 d2 u (x) d2 u (x)
V0 u (x) = Eu (x) ) + q 2 u (x) = 0; (8.178)
2m dx2 dx2
where
2m (E + V0 )
q2 = : (8.179)
~2
The general solutions of Eqs. (8.176) and (??) are given by
8
< Aeikx + Re ikx ; x< a
u (x) = Ceiqx + De iqx ; a<x<a (8.180)
:
T eikx ; x>a
where we dropped the e ikx term in the region x > a since there is nothing that
causes the particle to reverse its direction. However, in the regions x < a and
-a < x < a, the particle could get re‡ected because of the potential well and we
add the terms Re ikx and De iqx :The wave function and its derivative must
be continuous at x = a and x = a:This conditions can be combined and be
expressed as
1 du (x)
= continuous . (8.181)
u (x) dx
Thus at x = a, we …nd
k Ae ika Reika q Ce iqa

Deiqa
ika ika
= iqa + Deiqa
. (8.182)
Ae + Re Ce
Similarly at x = a
q Ceiqa De iqa
k ika q Ceiqa De iqa
= T e ) k = : (8.183)
Ceiqa + De iqa T eika Ceiqa + De iqa
We can solve these equations for R and T and express the solution in terms of
the incident wave amplitude A;
ie 2ika q 2 k 2 sin (2qa)

R = A;
2qk cos (2qa) i (q 2 + k 2 ) sin (2qa)
e 2ika 2qa
T = A: (8.184)
2qk cos (2qa) i (q 2 + k 2 ) sin (2qa)
The probability that the incident particle gets re‡ected at the well is given by
2 2
jre jRj q 2 k 2 sin2 (2qa)
= 2 = 2 2 ; (8.185)
jin jAj 4 (qk) cos2 (2qa) + (q 2 + k 2 ) sin2 (2qa)
and gets transmitted

2 2
jre jT j 4 (qk)
= 2 = 2 2 (8.186)
jin jAj 4 (qk) cos (2qa) + (q 2 + k 2 ) sin2 (2qa)
2
(i) i. E>>V : When the energy of the incident particle is much bigger than the
depth of the well, we have
2m (E + V0 ) 2mE
q2 = = = k2 : (8.187)
~2 ~2
which gives
2
jRj
2 = 0; (8.188)
jAj
and
2
jT j 4k 4
2 = =1 (8.189)
jAj 4k 4 cos2 (2ka) + sin2 (2qa)
The particle will never be re‡ected.
(ii) E !0 : When the energy of the incident particle approaches zero, we have
2m (E + V0 ) 2mV0 2 2mE
q2 = 2 = 2
;k = = 0:
~ ~ ~2
which gives
2
jRj q 4 sin2 (2qa)
2 = =1 (8.190)
jAj q 4 sin2 (2qa)
and
2
jT j
2 = 0: (8.191)
jAj
The particle will never be transmitted.
(iii) Selected energy values: when the energy of the incident particle equals to
a value which satis…es the condition
sin2 (2qa) = 0 ) 2qa = n ; n = 1; 2; 3:::
the probability of the particle being re‡ected becomes zero and the well
becomes completely transparent for the particle. This energy is given by
2m (E + V0 ) n2 2
2qa = n ) 4q 2 a2 = n2 2
) = (8.192)
~2 4a2
2 2 2
~ n
) E= V0 + :
8ma2
This is actually a model of what happens in the scattering of low en-
ergy electrons (0:01ev) by noble gas atoms-for example, neon and argon-in
which there is anomalously large transmission. In wave language, the ef-
fect is due to destructive interference between the wave re‡ected at x = a
and the wave re‡ected once twice, thrice,... at the edge x = a:
Negative Energy ( E < 0) and bound states: For this case as shown in the
…gure below the incident particle has a negative energy which is in fact possible
when the potential is an attractive potential. One example is a particle in a
gravitation …eld V (r) = GM m=r or the electron in a hydrogen atom V (r) =
e2 =4 0 r:The Schrödinger equation in the region x < a and x > a can be
written as
~2 d2 u (x) d2 u (x) 2
= jEj u (x) ) u (x) = 0;
2m dx2 dx2
where
2 2m jEj
= : (8.193)
~2
In the region a<x<a
~2 d2 u (x) d2 u (x)
V0 u (x) = jEj u (x) ) + q 2 u (x) = 0; (8.194)
2m dx2 dx2
where
2m (V0 jEj)
q2 = : (8.195)
~2
The general solutions of Eqs. (8.176) and (??) are given by
8
< Ae x ; x< a
u (x) = B cos (qx) + C sin (qx) ; a<x<a (8.196)
:
De x ; x>a
where we dropped the e x term in the region x < a and e x term in the region
x > a since the wave function diverges for x ! 1 and x ! 1;respectively.
using the combined condition for the continuity of the wave function and its
derivative
1 du (x)
= continuous . (8.197)
u (x) dx
at x = a, we …nd
a q [B sin (qa) + C cos (qa)] B sin (qa) + C cos (qa)

a
Ae = ) = .
Ae B cos (qa) C sin (qa) B cos (qa) C sin (qa) q
(8.198)
and at x = a
q [ B sin (qa) + C cos (qa)] a B sin (qa) + C cos (qa)
= a
Ae ) = .
B cos (qa) + C sin (qa) Ae B cos (qa) + C sin (qa) q
(8.199)
When the case C = 0 , we …nd
sin (qa)
= ) tan (qa) = . (8.200)
cos (qa) q q
and for the case B = 0,
cos (qa) q
= ) tan (qa) = (8.201)
sin (qx) q
Alternative approach: We may follow an alternative approach that we were
introduced in Theoretical Physics I to …nding the energy eigen values. To this
end we write the four boundary conditions independently. That mean at x =
a, we have
8
< Ae x ; x< a
u (x) = B cos (qx) + C sin (qx) ; a<x<a (8.202)
:
De x ; x>a
a a
Ae = B cos (qa) C sin (qa) ; Ae = q [B sin (qa) + C cos (qa)] ; (8.203)
and at x = a
a a
B cos (qa) + C sin (qa) = De ; q [ B sin (qa) + C cos (qa)] = De ;
(8.204)
a
Ae B cos (qa) + C sin (qa) = 0;
a
A e Bq sin (qa) Cq cos (qa) = 0;
a
B cos (qa) + C sin (qa) De = 0;
a
Bq sin (qa) + Cq cos (qa) + De = 0: (8.205)
Using matrices we can put these set of equations in the form
2 a
32 3
e cos (qa) sin (qa) 0 A
6 e a
q sin (qa) q cos (qa) 0 76 B 7
6 76 7
4 0 cos (qa) sin (qa) e a 5 4 C 5 = 0: (8.206)
a
0 q sin (qa) q cos (qa) e D
For a none trivial solution (i.e. A 6= 0; B 6= 0; C 6= 0; and D 6= 0), we recall

Cramer’s rule
a
e cos (qa) sin (qa) 0
a
e q sin (qa) q cos (qa) 0
det a =0
0 cos (qa) sin (qa) e
a
0 q sin (qa) q cos (qa) e
q sin (qa) q cos (qa) 0
a a
)e cos (qa) sin (qa) e
a
q sin (qa) q cos (qa) e
a
e q cos (qa) 0
a
+ cos (qa) 0 sin (qa) e
a
0 q cos (qa) e
a
e q sin (qa) 0
a
+ sin (qa) 0 cos (qa) e =0 (8.207)
a
0 q sin (qa) e
a a
a sin (qa) e cos (qa) e
)e q sin (qa) a + q cos (qa) a
q cos (qa) e q sin (qa) e
x a
a sin (qa) e 0 e
+ cos (qa) e x + q cos (qa) a
q cos (qa) e 0 e
a a
a cos (qa) e 0 e
+ sin (qa) e a + q sin (qa) a =0
q sin (qa) e 0 e
(8.208)
2 a
) qe f sin (qa) ( sin (qa) + q cos (qa)) + cos (qa) ( cos (qa) q sin (qa))g
2 a
+ e cos (qa) ( sin (qa) + q cos (qa))
2 a
+ e sin (qa) ( cos (qa) q sin (qa)) = 0
2 a 2
) qe sin (qa) q sin (qa) cos (qa) + cos2 (qa) q sin (qa) cos (qa)
+ e 2 a
sin (qa) cos (qa) + q cos (qa) + 2
sin (qa) cos (qa) q sin2 (qa) = 0
) 2e 2 a 2
q 2 sin (qa) cos (qa) + q cos2 (qa) sin2 (qa) = 0 (8.209)
There follows that

2
q 2 sin (qa) cos (qa) + q cos2 (qa) sin2 (qa) = 0
2 sin (qa) cos (qa)
) q2 q = 2
q2
cos (qa) sin (qa)
1 2
q tan (qa) =0) q 2 tan (qa) q tan2 (qa) 1
tan (qa)
q
= tan2 (qa) tan (qa) + tan (qa) 1=0
q
q
) tan (qa) tan (qa) + tan (qa)
q q
q q
= tan (qa) + tan (qa) = 0 ) tan (qa) = ; tan (qa) =
q q
(8.210)
Noting that
qa tan (qa) = a; qa cot (qa) = a. (8.211)
Using the explicit expressions for q and

r r
2m (V0 jEj) 2m jEj
q= ; = (8.212)
~2 ~2
and introducing the constant de…ned by
2mV0 a2
= (8.213)
~2
and the variable
r r
2ma2 (V0 jEj) 2ma2 jEj p
y = qa = ) a= = y2
~2 ~2
one can rewrite Eq. (8.211) as

p p
y2 y2
tan (y) = ; cot (y) = : (8.214)
y y
p
10 y 2
Figure 8.2: The graph colored red is f (y) = y and blue is f (y) = tan (y) :
These equations are transcendental equations and can only be solved graphically
as shown below. First let’s consider when = 10 (determined by the depth and
width of the well, and the mass of the particle); we have
p
10 y 2
tan (y) = :
y
as one can read from the graph; y = 2:48;which means when the potential energy
becomes
~2 ~2
V0 = = 5
2ma2 ma2
for = 10; the allowed total energy, using y = 1:18;one …nds
r
2m jEj a2 p ~2 ~2
2
= y2 ) E = y2 = 4:3 : (8.215)
~ 2ma2 ma2
In this case we …nd only one energy level. On the other hand for, = 200;
where
~2 ~2
V0 = 2
= 100 (8.216)
2ma ma2
there are …ve energy levels as one can determine the …ve allowed values for y
from the graph shown below
p
10 y 2
Figure 8.3: The graph colored red is f (y) = y and blue is f (y) = tan (y) :
2 2
~ y
n y En / ma2 = 2
1 1:43 98:98
3 4:43 90:19
5 7:29 73:43
7 10:14 48:59
9 13:00 15:10
On the other hand for the second possible solution we have
p
y2
cot (y) =
y
For = 200; we …nd another …ve possible values for y as shown in the …gure
~2
below.HW: Find the values for En / ma 2 corresponding to the second set of
solution.
The value of y at the intersection points are the accepted values (eigenvalues).
These
p forms a discreet set. The larger is, the further the graph for f (y) =
y2
y extends to the positive y. This occurs when the potential is deeper
and/or broader and in such cases we …nd more and more bound states. The
graphs also show that for the case
p
y2
tan (y) = (8.217)
y
no matter how small is, there will always be at least one bound state. This is
characteristic of one-dimensional attractive potentials and is not true for three-
dimensional potentials. Then the complete energy spectrum which is determined
p
10 y 2
Figure 8.4: The graph colored red is f (y) = y and blue is f (y) =
cot (y) :
by both solutions is shown in the …gure below from the lowest to the highest
energy state for = 200: As becomes larger, the eigenvalues tend to become
equally spaced in y, with the intersection points are given approximately
1
y= n+ ; n = 0; 1; 2:: (8.218)
2
On the other hand for the case (odd solution)

p p
y2 y2
cot (y) = ) tan ( =2 + y) =
y y
there will be a solution only when
p
2 =4 >0 (8.219)
and for large

y = n ; n = 1; 2; 3::: (8.220)
Figure
p 8.5: All the four graphes: Green (The graph colored red is f (y) =
10 y 2
and blue is f (y) = tan (y) :) and Red (The graph colored red is f (y) =
py
10 y 2
y and blue is f (y) = cot (y) :)
Chapter 9
The Harmonic oscillator
9.1 Classical Harmonic oscillator

A classical one-dimensional harmonic oscillator is an object with mass, m; at-
tached to a spring with spring constant, k; oscillating back and forth along one
speci…c direction on a frictionless surface (see Fig. 9.1)The classical Hamiltonian
Figure 9.1: One-dimensional Harmonic oscillator.
is given by
p2 1
H= + kx2 : (9.1)
2m 2
In terms of the angular frequency, !; de…ned as
r
k
!= (9.2)
m
223
224 CHAPTER 9. THE HARMONIC OSCILLATOR
the classical Hamiltonian can be expressed as

p2 1
H= + m! 2 x2 : (9.3)
2m 2
9.2 Quantum harmonic oscillator-using the Schrödinger

equation
The quantum Hamiltonian, H, ^ for a quantum Harmonic oscillator can be ob-
tained from the classical Hamiltonian by replacing the momentum with the
momentum operator p^
d
p ! i~ ; (9.4)
dx
which gives
2 2
^ = ~ d + 1 m! 2 x2 :
H (9.5)
2m dx2 2
Then the eigenvalue equation for a quantum harmonic oscillator becomes
^ (x) = Eu (x) ) ~2 d2 u (x) 1

Hu + m! 2 x2 u (x) = Eu (x)
2m dx2 2
~ d2 u (x) m! 2 2E
) + x u (x) = u (x) : (9.6)
!m dx2 ~ ~!
Introducing the dimensionless energy, ; and position, ; de…ned by
r r r
2E m! ~ ~
= ; = x)x= ; dx = d (9.7)
~! ~ m! m!
one can rewrite the energy eigenvalue equation as
d2 u ( ) 2
+ u ( ) = 0: (9.8)
d 2
To solve this equation we …rst …nd the asymptotic solution u0 ( ), for the case
2
! 1: For this case we can approximate the di¤erential equation as
d2 u0 2
u0 = 0 (9.9)
d 2
Multiplying this equation by 2 du
d , we may write
0
du0 d2 u0 2 du0 du0 d2 u0 2 du0

2 2u0 =0)2 2u0 =0
d d 2 d d d 2 d
2 2
d du0 2 du0
) =0
d d d
2
d du0 2
2 du0 d 2
) u20 + 2u20 = 0
d d d d
2 2 2
d du0 d u0
) + 2u20 = 0 (9.10)
d d d
9.2. QUANTUM HARMONIC OSCILLATOR-USING THE SCHRÖDINGER EQUATION225
2
For the case ! 1;
2 2
d u0
2 u20 << : (9.11)
d
we may make the approximation
# "
2 2 2 2
d du0 d u0 d
du0 2 2
=0) u0 = 0
d d d d
d
2 q
du0 2 2 du0
) u0 = C ) = C + 2 u20 ; (9.12)
d d
where C is a constant. Since the eigen function and its derivative must vanish
at in…nity, we must have
du0
u0 ( )j = 1 = = 0 ) C = 0; (9.13)
d = 1
This leads to
du0
= u0 ; (9.14)
d
the solution of which is given by
2
=2
u0 ( ) = Ae (9.15)
2
we drop the e =2 term since it leads to a diverging function at 1: Now using
the asymptotic solution which is valid when ! 1; we can write the solution
to the the exact eigenvalue equation
d2 u ( ) 2
+ u( ) = 0 (9.16)
d 2
as
2
=2
u( ) = h( )e ;
du ( ) 2
=2 dh ( ) 2
=2
) =e h( )e
d d
d2 u ( ) d 2
=2 dh ( ) d h 2
=2
i
) 2 = e h( )e
d d d d
d2 u ( ) 2
2
=2 d u ( ) 2
=2 dh ( ) 2
=2 dh ( ) 2
=2
) =e e h( )e e
d 2 d 2 d d
2 2
2 d u( ) d u( ) dh ( ) 2
+ 2h ( ) e =2
) = 2 + 2
h( ) h( ) e =2
d 2 d 2 d
(9.17)
Using these results the di¤erential equation
d2 u ( ) 2
+ u( ) = 0 (9.18)
d 2
can be rewritten as
d2 u ( ) dh ( ) 2 2 2
=2
2 + h( ) h( ) + h( ) e =0
d 2 d
which gives the di¤erential equation
d2 h ( ) dh ( )
2 + 2ph ( ) = 0; (9.19)
d 2 d
where
1
; p= (9.20)
2
which is known as the Hermit equation. We we were introduced how to solve such
kind of di¤erential equation (in Theoretical Physics I ) using series substitution
method.
We assume the solution can be expressed as power series
1
X
n
h( ) = an (9.21)
n=0
so that
1 1
dh ( ) X n 1
X
n
= an n = an+1 (n + 1) ;
d n=0 n=0
1 1
d2 h ( ) X n 1
X
n
) = an+1 (n + 1) = an+2 (n + 2) (n + 1) : (9.22)
d 2 n=0 n=0
Upon substituting these equations into the di¤erential equation, we …nd

1
X 1
X 1
X
n n n
an+2 (n + 2) (n + 1) 2 an n + 2p an =0 (9.23)
n=0 n=0 n=0
1
X
n
) [an+2 (n + 2) (n + 1) 2an (n p)] = 0: (9.24)
n=0
There follows that

2 (p n)
an+2 (n + 2) (n + 1) 2an (n p) = 0 ) an+2 = an (9.25)
(n + 2) (n + 1)
For even n, we have
2p 2 (p 0)
a2 = ao = a0 ; (9.26)
2 1 2!
2 (p 2) 22 (p 2) (p 0)
a4 = a2 = a0 ;
4 3 4!
2 (p 4) 23 (p 4) (p 2) (p 0)
a6 = a4 = a0 (9.27)
6 5 6!
2 (p 6) 24 (p 6) (p 4) (p 2) (p 0)
a8 = a6 = a0 (9.28)
8 7 8!
Therefore, the even terms are given by

n
( 2) p (p 2) (p 4) :: (p 2 (n 1))
a2n = a0 : (9.29)
(2n)!
And the even series can then be expressed as
( 1
)
X n
( 2) p (p 2) (p 4) :: (p 2 (n 1)) 2n
heven ( ) = a0 1 + : (9.30)
n=1
(2n)!
For odd n
2 (p 1) 2 (p 1)
a3 = a1 = a1 ;
3 2 3!
2 (p 3) 22 (p 1) (p 3)
a5 = a3 = a1 ;
5 4 5!
2 (p 5) 23 (p 1) (p 3) (p 4)
a7 = a5 = a1 (9.31)
7 6 7!
and the odd series can then be expressed as
( 1
)
X n
( 2) p (p 1) (p 3) ::: (p 2 (n 1)) 2n+1
hodd ( ) = a1 +
n=1
(2n + 1)!
If p is an even integer, we may express it as
p = 2m; (9.32)
where m is a positive integer, and the even series solution becomes

( 1 n
)
X ( 2) 22n 1 m (m 1) (m 2) ::: (m n 1) 2n
heven ( ) = a0 1 +
n=1
2n!
(9.33)
and this will terminate when
m n + 1 = 0: (9.34)
On the other hand when p is odd, we have
p = 2m 1 (9.35)
and the odd series can be rewritten as

( 1
)
X n
( 2) (2m) (2m + 2) (2m + 4) ::: (2m 2n) 2n
hodd ( ) = a1 +
n=1
(2n + 1)!
(9.36)
and this will terminate when m = n. Now let’s consider the …rst few terms.
Note that h0 ( ) is when n = 0 and that is given by the even series
ho ( ) = a0 (9.37)
h1 ( ) is when n = 1 and that is given by the odd series as the even series
becomes zero
h1 ( ) = a1 (9.38)
h2 ( ) is when n = 2 and should be given by the even series as the odd series
becomes zero
h2 ( ) = a0 1 p 2 : (9.39)
These are the Hermit polynomials, Hn (x) ; except the normalization constants
a0 and a1 :
Energy Eigenvalues: we recall that
1 1
p= ) =2 +p (9.40)
2 2
and the dimensionless energy eigen value is
2E
= : (9.41)
~!
Combining these two we may write the energy of a quantum Harmonic oscillator
as
1
E = ~! +p : (9.42)
2
Since for a non-diverging solution of the Hermit equation to exist, we have seen
that p must be either even or odd integers including zero. Therefore, the energy
of a quantum Harmonic oscillator must be quantized and is given by
1
E = ~! + n ; n = 0; 1; 2; 3::: (9.43)
2
This tells you the ground state energy is not zero. In fact you get
~!
E0 = : (9.44)
2
In a classical harmonic oscillator the ground state means when the spring is
un-streched (x = 0) and the speed, v = 0 which leads to zero energy.
E0 = 0: (9.45)
The energy di¤erence, E; between adjacent states n and n + 1 is given by

1 1 3~!
E = ~! +n+1 ~! +n ) E= (9.46)
2 2 2
which shows that the energy levels are equally spaced.
Energy eigenstates: we recall the energy eigenstates in terms of the dimen-
sionless variable de…ned as r
m!
= x (9.47)
~
are given by
2
=2
ul ( ) = hl ( ) e (9.48)
where hl ( ) is given by
( 1
)
X n
( 2) (2l) (2l + 2) (2l + 4) ::: (2l 2n) 2n
hl ( ) = a1 +
n=1
(2n + 1)!
when l is odd and

( 1 n
)
X ( 2) 22n 1
l (l 1) (l 2) ::: (l n 1) 2n
hl ( ) = a0 1+ (9.49)
n=1
(2n)!
when l is even. Constants a0 and a1 are determined from the normalization

condition
Z1 Z1
2
2
ul ( ) d = 1 ) Hl2 ( ) e d = 1
1 1
which gives
2
=2
ul ( ) = Hl ( ) e (9.50)
where
Z1
2 p
Hl ( ) e = 2n n! : (9.51)
1
Here are a few list of the Hermit Polynomials
H0 ( ) = 1;
H1 ( ) = 2 ;
2
H2 ( ) = 4 2;
3
H3 ( ) = 8 12 ;
4 2
H4 ( ) = 16 48 + 12;
3 3
H4 ( ) = 32 160 + 120 : (9.52)
Note that the energy eigen function of a Harmonic oscillator are orthogonal.
This can be easily proved as follows: We recall energy eigenvalue equation
~2 d2 u (x) 1
+ m! 2 x2 u (x) = Eu (x) : (9.53)
2m dx2 2
Since we now know that the energy eigenvalues and the corresponding eigen
functions depend on the quantum number n, we can write
d2 un m! 2 2mEn
2
+ x2 un = un (9.54)
dx ~2 ~2
for a di¤erent eigenvalue l, we can also write that

d2 ul m! 2 2mEl
+ x2 ul = u : (9.55)
dx2 ~2 ~2 l
Multiplying the …rst by ul and the second by un , we …nd
d2 un m! 2 2mEn
ul + x2 ul un = ul un (9.56)
dx2 ~2 ~2
and
d2 ul m! 2 2 2mEl
un 2
+ 2
x un ul = un ul : (9.57)
dx ~ ~2
Subtracting the above two equations, we …nd
d2 ul d2 un 2m (El En )
un ul = un ul : (9.58)
dx2 dx2 ~2
Integrating this equation
Z 1 Z 1
d2 u d2 un 2m (El En )
un 2l ul dx = un ul dx: (9.59)
1 dx dx2 ~2 1
Using integration by parts, we may write the integrals

Z 1 1 Z 1
d2 u du dun dul
un 2l dx = un l dx
1 dx dx 1 1 dx dx
Z 1 Z 1
d2 ul dun dul
) un 2 dx = dx (9.60)
1 dx 1 dx dx
du
since both un and dxl vanish at 1: Similarly, we have
Z 1 1 Z 1
d2 un dun dul dun
ul 2
dx = u l dx (9.61)
1 dx dx 1 1 dx dx
Z 1 Z 1
d2 un dul dun
) ul 2
dx = dx
1 dx 1 dx dx
so that Z 1
d2 ul d2 un
un ul dx = 0
1 dx2 dx2
In view of this results,
Z 1
2m (El En )
un ul dx = 0
~2 1
which shows that Z 1

0; l 6= n
un ul dx = (9.62)
1 1; l=n
when El 6= En :
9.3. THE HARMONIC OSCILLATORUSING THE LADDER OPERATORS231
9.3 The Harmonic oscillatorusing the ladder op-

erators
A. The Quantum Hamiltonian
We recall a classical Harmonic oscillator is described by the Hamiltonian
p2 1
H= + m! 2 x2 ; (9.63)
2m 2
where the angular frequency, !; is
r
k
!= : (9.64)
m
We can rewrite this Hamiltonian in dimensionless form as
H p2 m! 2
= + x (9.65)
~! 2m~! 2~
or r r
H m! p m! p
= x + ip x ip : (9.66)
~! 2~ 2m~! 2~ 2m~!
We want to determine the quantum form of this Hamiltonian in terms of an
operator, a
^; and its Hermitian conjugate, a ^y ; known as the ladder operators.
These operators, as we will see later, resembles the raising, J^+ ; and lowering J^
operators that we saw when in Chapter 4. These ladder operators are de…ned
in terms of the Hermitian momentum and position operators
r r
m! p^ y m! p^
a
^= ^ + ip
x )a ^ = ^ ip
x : (9.67)
2~ 2m~! 2~ 2m~!
We use these operators to obtain the quantum Hamiltonian for the Harmonic
oscillator. At this point we may tempted that the quantum Hamiltonian, which
we may write
r r
H^ m! p^ m! p^
= ^ + ip
x x^ ip : (9.68)
~! 2~ 2m~! 2~ 2m~!
or r r
H^ m! p^ m! p^
= x
^ ip ^ + ip
x : (9.69)
~! 2~ 2m~! 2~ 2m~!
can just simply be expressed as
H^
=a
â^y : (9.70)
~!
or
H^
^y a
=a ^: (9.71)
~!
Well this would have been correct if the operators a

^ and a ^y do commute. Let’s
…nd out if these operators do commute or not. To this end, we note that
r r
y m! p^ m! p^
a
^; a
^ = ^ + ip
x ; ^ ip
x
2~ 2m~! 2~ 2m~!
r
m! 1 1 m!
= [^
x; x
^] p; p^] i p
[^ f[^
p; x
^] + [^x; p^]g (9.72)
2~ 2m~! 2m~! 2~
Noting that
[^
x; x
^] = [^
p; p^] = 0; [^
p; x
^] = [^
x; p^] ; [^
x; p^] = i~; (9.73)
we …nd
1
a ^y =
^; a i(2i~) ) a ^y = 1:
^; a (9.74)
2~
which shows that the ladder operators do not commute! Therefore in such cases
we must …rst rewrite the quantum Hamiltonian as
r r
H^ 1 m! p^ m! p^
= ^ ip
x ^ + ip
x (9.75)
~! 2 2~ 2m~! 2~ 2m~!
r r
m! p^ m! p^
+ ^ + ip
x ^ ip
x : (9.76)
2~ 2m~! 2~ 2m~!
so that one …nds the correct quantum Hamiltonian
H^ 1 y 1
= a
^ a
^+a
â ^ = ~! a
^y ) H ^y a
^+ : (9.77)
~! 2 2
where we used the commutation relation
a ^y = 1 ) a
^; a â^y = a
^y a
^ + 1: (9.78)
Another alternative is to express the momentum and position operators in terms
of a ^y ,
^ and a p r
2m~! y 1 2~
p^ = a
^ a ^ ;x^= a
^+a ^y : (9.79)
2i 2 m!
and use the quantum Hamiltonian
H^ p^2 m! 2
= + x
^ (9.80)
~! 2m~! 2~
that leads to
"p #2 " r #2
H^ 1 2m~! m! 1 2~
= a
^ ^y
a + a ^y
^+a
~! 2m~! 2i 2~ 2 m!
H^ 1 2 1 2
) = a
^ a ^y + a
^+a ^y
~! 4 4
H^ 1 2 1 2
) = a
^ +a ^y2 a ^y a
â ^y a
^ + a
^ +a^y2 + a
â^y + a
^y a
^
~! 4 4
H^ 1 1
) = a
â^y + a
^y a
^ )H ^ = ~! a ^y a
^+ (9.81)
~! 2 2
B. The Energy Eigenvalues

The energy eigenvalues which we already determined by solving the Schrödinger
equation is given by
1
En = ~! n + ; where n = 0; 1; 2::: (9.82)
2
Next we …nd these eigenvalues using the quantum Hamiltonian we determined
in terms of the ladder operators. To this end, we derive two important commu-
tation relations
h i 1
^ a
H; ^y = ~! a ^y a
^+ ^y = ~! a
;a ^y a ^y
^; a (9.83)
2
h i 1
^ a
H; ^y a
^ = ~! a ^+ ;a ^y a
^ = ~! a ^; a
^ (9.84)
2
Using the relation h i h i h i
A^B; ^ C^ B
^ C^ + A;
^ C^ = A^ B; ^ (9.85)
we …nd
h i h i
^ a
H; ^y ^y a
= ~! a ^; a^y + a ^y ; a
^y a
^ ) H; ^ a^y = ~!ây
h i h i
^ a
H; ^ = ~! a ^y ; a
^ a ^ + [^
a; a
^] a^y ) H;^ a^ = ~!^ a (9.86)
Let’s consider the energy eigenstates jEi and E (1) = a

^ jEi with corresponding
eigenvalues E and E (1) : Then we can write the eigenvalue equations as
^ jEi = E jEi :
H (9.87)
and
^ (^
H a jEi) = E (1) (^
a jEi) : (9.88)
using the commutation relation
h i
^ a
H; ^ = ~!^ â =
a ) H^ a+a
~!^ ^H^ (9.89)
as
^ a jEi = a
H^ ^H^ a jEi = (^
~!^ aE a) jEi = (E
~!^ ~!) a
^ jEi
^ (^
)H a jEi) = (E ~!) (^
a jEi) (9.90)
Recalling that E (1) = a

^ jEi ; we …nd
E E
^ (^
H ^ E (1) = (E
a jEi) = H ~!) E (1)
This means the state E

E (1) = a
^ jEi : (9.91)
^ with eigenvalue
is an eigenstate of H
E (1) = E ~!
^ a on the eigenstate E (1) , we …nd

If we operate H^
E E E E
^ a E (1) = a
H^ ^H^ a
~!^ ^ a E (1) = E (1)
E (1) ) H^ ^ E (1) :
~! a
using E
E (1) = a
^ jEi ; E (1) = E ~! (9.92)
we …nd
E E
^ a
H ^2 jEi = (E 2~!) a ^ E (2) = (E
^2 jEi ) H 2~!) E (2) : (9.93)
where E
E (2) = a
^2 jEi : (9.94)
is the energy eigenstate with eigenvalue
E (2) = E 2~!: (9.95)
for the harmonic oscillator. This leads to the conclusion that the state
E
E (n) = a ^n jEi : (9.96)
^ with eigenvalue
is the energy eigenstate of H
En = E n~!: (9.97)
and every time a^ acts on the energy eigenstate jEi it lowers the energy eigenvalue
by one "it takes you down the energy ladder one step at a time". But eventually
you would reach the bottom of the ladder (the ground state energy). Can this
bottom be zero or negative? The answer to this question is it can’t be negative
and must be zero. We can show this using the fact that the momentum and
position operators (and therefore the Hamiltonian) are Hermitian
h j p^2 j i = p j p^ i > 0;
h j p^p^ j i = h^
^2 j i =
h jx h jx
^x^ j i = h^ ^ i > 0;
x jx (9.98)
which leads to
^ jEi = 1 hEj p^2 jEi + 1 m! 2 hEj x

hEj H ^ jEi > 0
^2 jEi ) hEj H
2m 2
This does not mean that the minimum energy is zero. It means there is a
state where we hit the bottom of the energy ladder and this energy can not
be negative. Let’s say this state be E (0) (the ground state); then since there
exists no state which can be the energy eigenstate we must have
E
^ E (0) = 0:
a (9.99)
Operating the Hamiltonian on the ground state,

E 1 E E 1 E
^ E (0)
H = ^y a
~! a ^+ ^y a
E (0) = ~! a ^ E (0) + E (0)
2 2
E ~! E
^ E (0) =
) H E (0) ; (9.100)
2
where we used E
^ E (0) = 0:
a (9.101)
This in fact shows that the ground state energy in fact is not zero and is given
by
~!
E (0) = : (9.102)
2
The is the result of the uncertainty principle. Suppose the oscillator is in the
minimum energy state, which is zero classically. The expectation values (the
most probable value of a measurement) of momentum and position are zero
h^
pi = h^
xi = 0: (9.103)
This leads to the uncertainties

2 2 2 2
( p) = p^2 pi = p^2 ; ( x) = x
h^ ^2 h^ ^2
xi = x (9.104)
and the expectation value for the ground state energy

D E 2
^ = p^ + 1 m! 2 x2
E (0) = H (9.105)
2m 2
becomes
2
( p) 1 2
E (0) = + m! 2 ( x) : (9.106)
2m 2
This means that unless
2 2
( p) = ( x) = 0 (9.107)
the ground state energy E0 can not be zero. Quantum mechanics (The Uncer-
tainty principle) forbids measuring the momentum and position simultaneously
with zero uncertainties in both observables.
C. The energy eigenstates
We have seen that the ladder operator, a ^; takes us down the energy eigen-
states (energy ladder) by one step measured by the energy changes, E = ~!:
This means if you have an energy eigenstate E (n) with a corresponding energy
eigenvalue; En = ~! n + 21 : When you operate the ladder operator a ^ on this
state, it changes this eigenstate to a new eigen state E (n 1) with energy eigen-
value, En 1 = ~! n 1 + 21 = ~! n 12 ; so that E = En En 1 = ~!:
Suppose we represent these eigenstate as
E E
E (n) = jni ; E (n 1) = jn 1i
then one can write

E E
^ E (n) = c (n) E (n
a 1)
)a
^ jni = c (n) jn 1i : (9.108)
where c (n) is some constant that we need to determine. But …rst we need to
…nd out what the other ladder operator, a^y ; does to a given energy eigenstate.
To this end, we prefer to begin with the ground state, E (0) = j0i ; where we
have E E
^ E (0) = ~! E (0) :
H (9.109)
2
using the commutation relation
h i
^ a
H; ^y = ~!^ ^ ay = ~!^
ay ) H^ ay + a ^
^y H
E E ~! E
^ ay E (0) = ~!^
) H^ ay + a ^
^y H E (0) = ~! + ^y E (0)
a
2
E ~! E
^ a
)H ^y E (0) = ~! + ^y E (0) :
a (9.110)
2
This means the state E E

^y E (0) :
E (1) = a (9.111)
^ with eigenvalue
is an eigenstate of H
~!
E (1) = ~! + (9.112)
2
or E E
^ E (1) = E (1) E (1) :
H (9.113)
^ ay in the new eigenstate E (1) ,

Let’s operate H^
E E E E
^ ay E (1) = a
H^ ^ + ~!^
^y H ay ^ ay E (1) = E (1) + ~! a
E (1) ) H^ ^y E (1) :
so that using
E E ~!
^y E (0) ; E (1) =
E (1) = a + ~! (9.114)
2
we …nd
E E ~! E
^ ay E (1) = H
H^ ^ a
^y2 E (0) = + 2~! ^y2 E (0)
a : (9.115)
2
or E E
^ E (2) = ~!
H + 2~! E (2) : (9.116)
2
where E E
^y2 E (0) ; :
E (2) = a (9.117)
is the energy eigenstate with energy eigenvalue
1
E (2) = ~! 2 + : (9.118)
2
This leads to the conclusion that the energy eigenstates are given by
E
^yn E (0)
jE n i = C (n) a (9.119)
with a corresponding energy eigenvalues

1
E n = ~! n + ; (9.120)
2
where n = 0; 1; 2; 3::: and C (n) is the normalization factor. Now having seen
that n is an integer and a ^ lowers and a ^y raises the energy eigenstate by one,
if we represent the ground energy eigenstate by j0i ; we may write the energy
eigenstate as
^yn j0i
jE n i = jni = C (n) a (9.121)
so that
2
hE n j E n i = hn jni = jC (n)j h0j a ^yn j0i = 1
^n a (9.122)
For n = 0, obviously C (0) = 1: For n = 1, we have
2
jC (1)j h0j a
â^y j0i = 1 (9.123)
and using
1 1 H^ 1
a
â^y = a
^y a
^+1= ^y a
a ^+ + )a
â^y = +
2 2 ~! 2
we …nd
! " #
2 H^ 1 2
^ j0i 1
h0j H
jC (1)j h0j + j0i = 1 ) jC (1)j + =1
~! 2 ~! 2
2 1 1 1
) jC (1)j + = 1 ) C (1) = : (9.124)
2 2 1!
For n = 2
!
2 H^ 1
jC (2)j h0j a ^y2 j0i = 1 ) h0j a
^2 a ^y2 j0i = h0j a
^2 a ^ + ^y j0i
a
~! 2
h0j a ^ ay j0i 1
^H^
) h0j a ^y2 j0i =
^2 a + h0j a
â^y j0i (9.125)
~! 2
and using the result we obtained earlier
^ ay j0i = ~!
H^ ~! + ^y j0i
a (9.126)
2
we …nd
h0j a ^y2 j0i = 2 h0j a
^2 a â^y j0i = 2
where we used the result for n = 1
h0j a
â^y j0i = 1 (9.127)
and we …nd for the normalization constant

1
C (2) = p : (9.128)
2!
For n = 3
!
2 H^ 1
3 y3 3 y3 2
jC (3)j h0j a
^ a
^ j0i = 1 ) h0j a
^ a
^ j0i = h0j a
^ + ^y2 j0i
a
~! 2
^ ay2 j0i 1
^2 H^
h0j a
) h0j a ^y3 j0i =
^3 a ^2 a
+ h0j a ^y2 j0i (9.129)
~! 2
and using the result
^ ay = ~!^
H^ ay + a ^
^y H
we have
^ ay2 = ~!^
H^ ay2 + a ^ ay
^y H^
so that using
^ ay j0i = ~!
H^ ~! + ^y j0i
a (9.130)
2
we can write
h0j a ^ ay2 j0i = h0j a
^2 H^ ^2 ~!^ ay2 + a ^ ay j0i
^y H^ (9.131)
h i
) h0j a ^ ay2 j0i = ~! h0j a
^2 H^ ^y2 j0i + h0j a
^2 a ^ ay j0i
^y H^
^2 a
^ ay2 j0i = ~! h0j a ~!

^2 H^
) h0j a ^y2 j0i + h0j a
^2 a ^y ~! +
^2 a ^y j0i
a
2
^ ay2 j0i = ~! h0j a 3~! 5~!

^2 H^
) h0j a ^y2 j0i +
^2 a h0j a ^y2 j0i =
^2 a h0j a ^y2 j0i
^2 a
2 2
Using this result we can then write
^ ay2 j0i 1
^2 H^
h0j a
h0j a ^y3 j0i =
^3 a ^2 a
+ h0j a ^y2 j0i (9.132)
~! 2
as
h0j a ^y3 j0i = 3 h0j a
^3 a ^y2 j0i = 6
^2 a (9.133)
where we used the result for n = 2 and we …nd for the normalization constant
2 1 1
) jC (3)j = ) C (2) = p : (9.134)
6 3!
Therefore one can easily generalize that
1
C (n) = p : (9.135)
n!
and the normalized energy eigen functions can be expressed as
1 yn
jE n i = p a ^ j0i : (9.136)
n!
If we denote this state by jni, then based from what have seen about a ^y ,
^ and a
we can write p
a
^ jni = n jn 1i
and p
^y jni =
a n + 1 jn + 1i
so that p p p
^y a
a ^ jni = ay jn
n^ 1i = ^y a
n n jni ) a ^ jni = n jni
The operator
^ =a
N ^y a
^
is called the number operator. In terms of the number operator the Hamiltonian
can be written as
^ jni = ~! a 1 ^+1 ^ jni = ~! n + 1

H ^y a
^+ jni = ~! N jni ) H jni :
2 2 2
D. Back to Schrödinger equation
The ground state eigen function: Let’s consider the ground state j0i such
that
hxj a
^ j0i = 0: (9.137)
Using r
m! p^
a
^= ^ + ip
x (9.138)
2~ 2m~!
we can write
r r
m! p^ m! i
hxj ^ + ip
x j0i = 0 ) ^ j0i + p
hxj x hxj p^ j0i = 0:
2~ 2m~! 2~ 2m~!
(9.139)
Using the completeness relation for position eigenstates
Z1
dx0 jx0 i hx0 j = 1 (9.140)
1
we can write
Z1 Z1
0
hxj x ^ jx i hx j 0i = dx0 x0 hxj x0 i hx0 j 0i
^ j0i = dx hxj x 0 0
(9.141)
1 1
We recall
hxj x0 i = (x x0 ) ; hx0 j 0i = u0 (x0 )
where
u0 (x0 ) = hx0 j 0i
is the ground state energy eigen function, then
Z1
^ j0i = dx0 x0 (x
hxj x x0 ) u0 (x0 ) = xu0 (x)
1
Similarly for the momentum using

Z1
dp0 jp0 i hp0 j = 1 (9.142)
1
we can write
Z1 Z1
hxj p^ j0i = dp hxj p^ jp i hp j 0i = dp0 p0 hxj p0 i hp0 j 0i
0 0 0
(9.143)
1 1
We recall
1 0
hxj p0 i = up (x) = p eip x=~
2 ~
so that
Z1
hxj p j0i = dp0 p0 hxj p0 i hp0 j 0i (9.144)
1
becomes
Z1 Z1
1 0 @ 1 0
hxj p j0i = dp0 p0 p eip x=~ hp0 j 0i = i~ dp0 p eip x=~ hp0 j 0i :
2 ~ @x 2 ~
1 1
(9.145)
Now replacing
1 0
hxj p0 i = p eip x=~
2 ~
we …nd
Z1
@ @ @u0 (x)
hxj p j0i = i~ dp0 hxj p0 i hp0 j 0i = i~ hxj 0i = i~
@x @x @x
1
Therefore we can write the equation

r
m! i
^ j0i + p
hxj x hxj p^ j0i = 0: (9.146)
2~ 2m~!
as
r
m! ~ du0 (x)
xu0 (x) + p =0
2~ 2m~! dx
du0 (x) m! h m! 2 i
) = xdx ) u0 (x) = C0 exp x (9.147)
u0 (x) ~ 2~
Using the normalization condition for the energy eigen functions
Z1
dxu0 (x) u0 (x) = 1 (9.148)
1
we …nd the constant

m! 1=4
C0 =
~
and the normalized energy eigen function for the ground state becomes
m! 1=4 h m! 2 i
u0 (x) = exp x (9.149)
~ 2~
To …nd the eigen functions for the nth state we use
1 yn
jE n i = p a ^ j0i : (9.150)
n!
which gives
1 1 yn
^yn j0i ) un (x) = p a
un (x) = hx jE n i = p hxj a ^ u0 (x) :
n! n!
^y
where a r
m! p^
^y =
a x
^ ip : (9.151)
2~ 2m~!
is expressed as r
y m! ~ d
a
^ = x+ p : (9.152)
2~ 2m~! dx
In general for the Hamiltonian operator
2
^ = p^ + V (x)
H (9.153)
2m
we have
2
^ jEi = hxj p^ jEi + hxj V (x) jEi
hxj H (9.154)
2m
and using
^ jEi = E jEi ; hxj V (x) jEi = V (x) hx jEi
H
we can write
hxj p^2 jEi
E hx jEi = + V (x) hx jEi : (9.155)
2m
We note that the energy eigen function is
u (x) = hx jEi (9.156)
and show that

Z1 Z1
0 2 0 0
hxj p^ jEi = dp hxj p^ jp i hp j jEi = dp0 p02 hxj p0 i hp0 j jEi
2
1 1
Z1 Z1
0 02 1 ip0 x=~ 1 0
= dp p p e 0
hp j jEi = dp0 p02 p eip x=~ hp0 j jEi
2 ~ 2 ~
1 1
Z1 2 2 Z1
2 @ 0 1 ip0 x=~ 0 2 @
= ( i~) dp p e hp j jEi = ( i~) dp0 hxj p0 i hp0 j jEi
@x2 2 ~ @x2
1 1
2 2
2 @ d
) hxj p^2 jEi = ( i~) hxj Ei = ~2 u (x) (9.157)
@x2 dx2
The the equation
hxj p^2 jEi

E hx jEi = + V (x) hx jEi : (9.158)
2m
gives the time independent Schrödinger equation
~2 d2
u (x) + V (x) u (x) = Eu (x) : (9.159)
2m dx2
Example 2 Calculate
^2 jni
hnj x (9.160)
and
hnj p^2 jni (9.161)
using the ladder operators a ^y :
^ and a
Example 3 Solve the Haisenberg equation of motion for the operators a
^ and
^y for the Harmonic Oscillator.
a
Chapter 10
Orbital angular momentum

and hydrogenic atoms
10.1 Classical angular momentum

In classical mechanics a particle of mass, m; with momentum, p~; located at a
position described by the position vector ~r , its angular momentum is de…ned
as
~ = ~r p~:
L (10.1)
Figure 10.1: Orbital and spin angular momentum in classical mechanics.
243
244CHAPTER 10. ORBITAL ANGULAR MOMENTUM AND HYDROGENIC ATOMS
Angular momentum and central force …eld : In a central force …eld (such as
gravitational and electrical force …elds) the potential energy does not depend
on direction of the position vector ~r. It depends only on the magnitude of the
position vector, r. Then in such …elds the angular momentum is conserved
which means L ~ is a constant of motion
~
dL
= 0: (10.2)
dt
You most likely have shown this in classical mechanics class. If not, we can
easily show this. We note that
~
dL d d~r d~
p
= (~r p~) = p~ + ~r (10.3)
dt dt dt dt
so that using
d~r d~r
~v = ; p~ = m~v ) p~ = ~v m~v = m~v ~v = 0 (10.4)
dt dt
we …nd
~
dL d~
p
= ~r : (10.5)
dt dt
If the force is central, we have
d~
p ~r d~
p ~r
= F (r) r^ = F (r) ) ~r = F (r) ~r =0 (10.6)
dt r dt r
which leads to
~
dL d~
p ~
dL
= ~r =0) = 0; (10.7)
dt dt dt
This shows that the angular momentum is conserved.
10.2 Quantum orbital angular momentum

As we have seen in the previous chapters the transition from classical to quantum
is achieved by replacing both, ~r and p~ , with corresponding operators, b ~r and b
p~;
respectively: Thus the orbital angular momentum operator can be expressed as
~b = b
L ~r b bx i + L
p~ = L by j + L
b z k: (10.8)
In Cartesian coordinates, this can be expressed as
~b = (^
L xi + y^j + z^k) (^
px i + p^y j + p^z k)
~b = (^
)L y p^z z^p^y ) i + (^z p^x x ^p^z ) + (^xp^y y^p^x ) k (10.9)
b
~ =L bx i + L by j + Lb z k;
)L (10.10)
10.2. QUANTUM ORBITAL ANGULAR MOMENTUM 245
where Lbx ; L
b y ; and L
b z are the three components of the angular momentum op-
erators given by
b x = y^p^z
L b y = z^p^x
z^p^y ; L x bz = x
^p^z ; L ^p^y y^p^x (10.11)
We have shown that the angular momentum for a central force …eld is conserved.
As this conservation law is also true in quantum mechanics, we must have
~b
dL
= 0: (10.12)
dt
The angular Momentum and the Hamiltonian Operators: For a particle of
mass m in a three-dimensional potential …eld, the quantum Hamiltonian is given
by
2
H^ = p^ + V (~r) : (10.13)
2m
We recall the Haisenberg equation of motion for an operator, A^ (t)
d ^ i h^ ^ i
A (t) = H; A (t) ; (10.14)
dt ~
so that for the orbital angular momentum, which is a conserved quantity, we
…nd
dL~b i ^ ~b
= H; L = 0 ) H; ~b = 0:
^ L (10.15)
dt ~
The angular momentum operator commutes with the quantum Hamiltonian.This
is an an important property that we shall exploit to …nd the eigenvalues and
eigen functions for a 3D quantum problems involving a central force …eld such
the electron in a Hydrogen atom.
The angular momentum commutation relations: the components of the lin-
ear momentum operators commutes
[^
px ; p^y ] = [^
px ; p^z ] = [^
pz ; p^y ] = 0: (10.16)
But the components of the angular momentum operators do not commute.

h i
^x; L
L ^ y = [^
y p^z z^p^y ; z^p^x x
^p^z ]
= [^
y p^z z^p^y ; z^p^x ] [^
y p^z z^p^y ; x
^p^z ]
h i
^x; L
L ^ y = [^
y p^z ; z^p^x ] [^
z p^y ; z^p^x ] [^
y p^z ; x
^p^z ] + [^
z p^y ; x
^p^z ] (10.17)
Noting that
[^
z p^y ; z^p^x ] = [^
y p^z ; x
^p^z ] = 0
we …nd h i
L^x; L
^ y = [^
y p^z ; z^p^x ] + [^
z p^y ; x
^p^z ] : (10.18)

h i h i h i
A^B;
^ C^ = A^ B;
^ C^ + A;
^ C^ B^ (10.19)
we have
[^
y p^z ; z^p^x ] = y^ [^
pz ; z^p^x ] + [^
y ; z^p^x ] p^z = y^ [^
pz ; z^p^x ] = y^ [^
z p^x ; p^z ]
) [^
y p^z ; z^p^x ] = y^ f^
z [^
px ; p^z ] + [^
z ; p^z ] p^x g = y^ [^
z ; p^z ] p^x = i~^
y p^x (10.20)
similarly we can show that
[^
z p^y ; x
^p^z ] = i~^
xp^y : (10.21)
Therefore h i
^x; L
L ^ y = i~^
xp^y i~^ ^z
y p^x = i~L (10.22)
Following the same procedure we can show that
h i h i
L^y; L
^ z = i~L
^x; L^z; L
^ x = i~L
^y: (10.23)
On the other hand these components commute with the square of the total
angular momentum operator, L^2
h i h i h i
^x; L
L ^2 = L^y; L
^2 = L^z; L
^ 2 = 0: (10.24)
We have seen that the components of the angular momentum operator do not
commute with each other (i.e. with L) ^ but they do commute with the square of
the angular momentum operator L ^ 2 : This means that we can …nd a simultaneous
eigenstates for the components and L ^2:
10.3 The orbital angular momentum eigen func-

tions
In chapter four we have solved the angular momentum eigenvalue problem ap-
^ 2 ;and the
plying the fact that the square of the angular momentum operator, L
z-component, L ^ z commutes. We found the solution to be
^ 2 jl; mi = ~2 l(l + 1) jl; mi ; L
L ^ z jl; mi = ~m jl; mi (10.25)
where l = 0; 1; 2; 3::: and
l m l: (10.26)
In this section we seek to …nd the angular momentum eigen functions. To this
end, we recall some basic relations we determined in chapter four that invloves
theRaising and Lowering angular momentum operators
h i
^
L = L ^ x iL^y; L^+; L
^ = 2~L ^z;
^2
L ^+L
= L ^ +L ^ 2 ~L
^z;
h i h iz
L^2; L
^ = 0; L^z; L
^ = ~L ^ : (10.27)
10.3. THE ORBITAL ANGULAR MOMENTUM EIGEN FUNCTIONS 247
We want to determine the general form of the angular momentum eigen func-
tion, f ( ; ') = h ; ' jl; mi ; as we shall see shortly this functions are the Spher-
ical Harmonics, Ylm ( ; ') . To this end, we recall (from Theoretical physics I )
the relation between Cartesian and spherical coordinates
x = r sin ( ) cos (') ; y = r sin ( ) sin (') ; z = r cos ( )
so that using the angular momentum operators
Figure 10.2: Spherical Coordinates
b x = y^p^z @ @ b y = z^p^x @ @
L z^p^y = i~ y^ z^ ;L x
^p^z = i~ z^ x
^ ;
@z @y @x @z
bz = x @ @
L ^p^y y^p^x = i~ x
^ y^ ; (10.28)
@y @x
and applying the techniques we were introduced for transforming di¤erential
equations from one set of coordinate to another, one can show that, in spherical
coordinates,
b =L
^x ^ y = ~e i' @ @ bz = ~ @
L iL + i cot ( ) ;L : (10.29)
@ @' i @'
Applying these results and the relation
^2 = L
L ^+L
^ +L
^ 2z ^z;
~L
we can show that
b2 = @2 @ 1 @2
L ~2 2 + cot ( ) @ + 2 ; (10.30)
@ sin ( ) @'2
which is the angular momentum operator squared, in spherical coordinates.

Since the angular variables are continuos variables the completeness relation
is given by Z
d d' sin ( ) j ; 'i h ; 'j = 1: (10.31)
and the orthonormality condition is

0 0
sin ( ) ; '0 j ; 'i = (' '0 ) : (10.32)
From the momentum eigenvalue equation
^ 2 jl; mi = ~2 l(l + 1) jl; mi
L (10.33)
using the completeness relation for the angular variables, we may write
Z
^ 2 0 ; '0
d 0 d'0 sin 0 L 0
; '0 jl; mi = ~2 l(l + 1) jl; mi (10.34)
Introducing the functions de…ned by

0 0
Ylm ; '0 = ; '0 jl; mi ; (10.35)
one can write
Z
d 0 d'0 sin 0 ^ 2 Ylm
L 0
; '0 0
; '0 = ~2 l(l + 1) jl; mi (10.36)
and substituting the operator
b2 = @2 @ 1 @2
L ~2 2 + cot ( ) @ + 2 (10.37)
@ sin ( ) @'2
we may write
Z !
@2 @ 1 @2
d 0 d'0 sin 0
+ cot 0
0 + 0 Ylm 0
; '0 0
; '0
@ 02 @ sin2 @'02
(10.38)
2
= ~ l(l + 1) jl; mi (10.39)
multiplying by the bra-vector h ; 'j, one can write
Z !
0 0 0 @2 0 @ 1 @2 0 0
d d' sin + cot + Ylm ; '0 h ; ' ; '0
@ 02 @ 0 sin2 0
@'02
= ~2 l(l + 1) h ; ' jl; mi (10.40)
or
Z !
0 0 @2 0 @ 1 @2 0 0
d d' + cot + Ylm ; '0 (' '0 )
@ 02 @ 0 sin2 0
@'02
= ~2 l(l + 1)Ylm ( ; ') (10.41)
10.4. THE SCHRÖDINGER EQUATION AND THE ORBITAL ANGULAR MOMENTUM249
where we used
Ylm ( ; ') = h ; ' jl; mi
and the relation
0 0
sin ( ) ; '0 j ; 'i = (' '0 ) : (10.42)
Using the property of the Dirac-delta function, one …nds
@2 @ 1 @2
2 + cot ( ) @ + 2 Ylm ( ; ') = ~2 l(l + 1)Ylm ( ; ')
@ sin ( ) @'2
10.4 The Schrödinger equation and the orbital

angular momentum
Three-dimensional Schrödinger Equation: we recall that in Cartesian coordi-
nates the time independent Schrödinger Equation for a particle of mass, m;
with a one dimension potential energy V (x) is given by
~2 d2
(x) + V (x) (x) = E (x) : (10.43)
2m dx2
For three dimensional case this can be written as
~2 @2 @2 @2
+ + (x; y; z) + V (x; y; z) (x; y; z) = E (x; y; z) :
2m @x2 @y 2 @z 2
(10.44)
or
~2 2
r (x; y; z) + V (x; y; z) (x; y; z) = E (x; y; z) (10.45)
2m
where
@2 @2 @2
r2 = 2
+ 2+ 2 (10.46)
@x @y @z
is the Laplacian. In spherical coordinates
x = r sin ( ) cos (') ; y = r sin ( ) cos (') ; z = r cos ( ) :
the Laplacian can be expressed as
@2 2 @ 1 @2 @ 1 @2
r2 = + + 2 + cot ( ) + (10.47)
@r 2 r @r r @ 2 @ sin2 ( ) @'2
We recall that the square of the angular momentum is given by
b2 = @2 @ 1 @2
L ~2 2 + cot ( ) @ + 2 (10.48)
@ sin ( ) @'2
so that in terms of the angular momentum operator in spherical coordinates,

the Laplacian
@2 2 @ 1 @2 @ 1 @2
r2 = + + + cot ( ) + (10.49)
@r2 r @r r2 @ 2 @ sin2 ( ) @'2
can be expressed as
@2 2 @ b2
L
r2 = + : (10.50)
@r2 r @r ~2 r 2
Then the Schrödinger Equation
~2 2
r (x; y; z) + V (x; y; z) (x; y; z) = E (x; y; z)
2m
in spherical coordinates can be written as
" #
~2 @ 2 2 @ b2
L
+ (r; ; ') + V (r; ; ') (r; ; ') = E (r; ; ')
2m @r2 r @r ~2 r2
The Central Potential : when the potential energy depends only on the vari-
able, r; the potential is said to be central and we can write
V (r; ; ') = V (r) : (10.51)
For such potential the Schrödinger Equation in spherical coordinates becomes

" #
~2 @ 2 2 @ b2
L
+ (r; ; ') + V (r) (r; ; ') = E (r; ; ')
2m @r2 r @r ~2 r2
and it can be solved using separation of variables. For a central potential the
Hamiltonian (energy operator)
" #
~ 2
@ 2
2 @ Lb2
^ =
H + + V (r) (10.52)
2m @r2 r @r ~2 r2
b 2 commutes
and the angular momentum operator L
h i
^ L
H; b 2 = 0; (10.53)
we can …nd a simultaneous eigen function. Since we already know the eigenvalue
b 2 , which is given by
equation for L
b 2 Ylm ( ; ') = ~2 l (l + 1) Ylm ( ; ') :
L (10.54)
where Ylm ( ; ') are the spherical Harmonics. Therefore, for energy eigenvalue
equation (the Schrödinger Equation)
^ (r; ; ') = E (r; ; ')
H (10.55)
10.5. HYDROGENIC ATOMS 251
the energy eigen function (r; ; ') can be expressed as
(r; ; ') = Rnl (r) Ylm ( ; ') (10.56)
b 2 :Now substituting this into

^ and L
which is a simultaneous eigen function to H
the Schrödinger Equation, we …nd
^ nl (r) Ylm ( ; ') = Enl Rnl (r) Ylm ( ; ')
HR (10.57)
~2 d2 Rnl (r) 2Ylm ( ; ') dRnl (r)

Ylm ( ; ') +
2m dr2 r dr
b 2 Ylm ( ; ')
Rnl (r) L
+ + V (r) Rnl (r) Ylm ( ; ') = Enl Rnl (r) Ylm ( ; ')
r2 2m
(10.58)
Using the result

b 2 Ylm ( ; ') = ~2 l (l + 1) Ylm ( ; ')
L (10.59)
we may write
~2 d2 Rnl (r) 2 dRnl (r) Rnl (r) ~2 l (l + 1) Ylm ( ; ')

+ Ylm ( ; ') +
2m dr2 r dr r2 2m
+V (r) Rnl (r) Ylm ( ; ') = Enl Rnl (r) Ylm ( ; ') (10.60)
which can be simpli…ed into
~2 d2 Rnl (r) 2 dRnl (r) Rnl (r) ~2 l (l + 1)

2
+ + + V (r) Rnl (r) = Enl Rnl (r)
2m dr r dr r2 2m
(10.61)
d2 Rnl (r) 2 dRnl (r) l (l + 1) Rnl (r) 2mV (r) 2mEnl
+ Rnl (r) = Rnl (r)
dr2 r dr r2 ~2 ~2
(10.62)
d2 Rnl (r) 2 dRnl (r) 2mEnl 2mV (r) l (l + 1)
+ + Rnl (r) = 0 (10.63)
dr2 r dr ~2 ~2 r2
This is the equation we need to solve for any central force …eld.
10.5 Hydrogenic atoms

A hydrogenic atom is an atom that has z protons in the nucleus and one elec-
trons. This single electron located at a distance r from the nucleus experiences
an attractive electostatic force. The electostatic potential energy is central and
is given by
1 Ze2
V (r) = : (10.64)
4 0 r
For such potential energy the Schrödinger Equation we derived earlier
Figure 10.3: A Hydrogenic atom (Z protons at the Nucleus and an electron at

a position described by spherical coordinates (r; ; '):
d2 Rnl (r) 2 dRnl (r) 2mEnl 2mV (r) l (l + 1)

+ + Rnl (r) = 0 (10.65)
dr2 r dr ~2 ~2 r2
becomes
d2 Rnl (r) 2 dRnl (r) 2m Ze2 1 ~2 l (l + 1)
2
+ + 2 Enl + Rnl (r) = 0: (10.66)
dr r dr ~ 4 0r 2mr2
We are interested in the dynamics of the electron when it is bound to the nucleus.
For such conditions the total energy is negative and we can write
d2 Rnl (r) 2 dRnl (r) 2m Ze2 1 ~2 l (l + 1)
+ + 2 jEnl j + Rnl (r) = 0:
dr2 r dr ~ 4 0r 2mr2
d2 Rnl (r) 2 dRnl (r) 2m ~2 l (l + 1) Ze2 1
2
+ 2
jEnl j + Rnl (r) = 0:
dr r dr ~ 2mr2 4 0r
Introducing the dimensionless variable
r
8m jEnl j
= r (10.67)
~2
we have
r ! 1 r ! 2
8m jEnl j 2 8m jEnl j
dr = d ) dr = d 2; (10.68)
~2 ~2
so that the di¤erential equation becomes

r
d2 Rnl ( ) 2 dRnl ( ) 1 l (l + 1) m Ze2 1
+ + Rnl ( ) = 0:
d 2 d 4 2 2 jEnl j 4 0 ~
(10.69)
or
d2 Rnl ( ) 2 dRnl ( ) l (l + 1) 1
+ Rnl ( ) + Rnl ( ) = 0: (10.70)
d 2 d 2 4
where r
m Ze2
= : (10.71)
2 jEnl j 4 0 ~
The energy spectrum: to determine the energy eigenvalues we need to solve
the second order di¤erential equation we derived above. To this end, we …rst
…nd the asymptotic solution, ! 1: For this case the di¤erential equation can
be approximated as
d2 Rnl
0
( ) 1 0
R ( )=0 (10.72)
d 2 4 nl
and the solution of which is given by
0 =2
Rnl ( ) = Ae ; (10.73)
where we took into account the fact that 0: In terms of this asymptotic
solution the general solution can be expressed as
=2
Rnl ( ) = G ( ) e : (10.74)
For this function, we have
dRnl ( ) dG ( ) G ( )
= e =2 ; (10.75)
d d 2
d2 Rnl ( ) d2 G ( ) 1 dG ( ) 1 dG ( ) G ( ) =2
2
= + e (10.76)
d d 2 2 d 2 d 4
so that substituting Eqs. (10.74)-(10.76) into Eq. (10.70), we …nd
d2 G ( ) 2 dG ( ) 1 l (l + 1)
1 + G ( ) = 0: (10.77)
d 2 d 2
One more asymptotic solution is to consider ! 0, for this case we may ap-
proximate the above equation as
d2 G0 ( ) 2 dG0 ( ) l (l + 1)
+ G0 ( ) = 0: (10.78)
d 2 d 2
The solution of this DE can be determined using power series substitution

method. Using this method we have determined the solution to such DE in
Theo. Phys. I (Section 13.3), which found to be
C
G0 ( ) = B l
+ l+1
: (10.79)
However, for a hydrogenic atoms since the eigen function must be de…ned in-
cluding the nucleus ( = 0) and the acceptable assymptotic solution should then
be
G0 ( ) = B l : (10.80)
Therefore, one can express the exact function, G ( ) ; as
dG ( )
l dH ( ) l
G( ) = H ( ) =) + l l 1H ( ) (10.81)
d d
d2 G ( ) d2 H ( ) l dH ( ) l 1
) 2
= 2
+2 l + l (l 1) l 2 H ( ) (10.82)
d d d
Substituting Eqs. (10.80)-(10.82) into Eq. (10.77) and simplifying the resulting
expression, one …nds
d2 H ( ) 2 (l + 1) dH ( ) l 1
+ 1 + H ( ) = 0: (10.83)
d 2 d
We now use a series substitution method to solve this equation. To this end,
we note that
1
X 1 1
k dH ( ) X k 1 d2 H ( ) X k 2
H( )= ak ) = ak k ) = ak k (k 1) ;
n=0
d d 2
k=0 k=0
(10.84)
so that upon substituting these expressions into Eq. (10.83), one …nds
1
X 1
X 1
X
k 2 2 (l + 1) k 1 l 1 k
ak k (k 1) + 1 ak k + ak = 0;
k=0 k=0 k=0
(10.85)
1
X 1
X
k 2 k 1
ak k (2l + k + 1) +( l 1 k) ak = 0: (10.86)
k=0 k=0
Noting that
1
X 1
X
k 2 k 1
ak k (2l + k + 1) = ak+1 (k + 1) (2l + k + 2) (10.87)
k=0 k=0
one can rewrite Eq. (10.86) as

1
X
k 1
fak+1 (k + 1) (2l + k + 2) + ak ( l 1 k)g = 0: (10.88)
k=0
There follows that

ak+1 (k + 1) (2l + k + 2) + ak ( l 1 k) = 0
ak+1 k+l+1
) = ; (10.89)
ak (k + 1) (2 (l + 1) + k)
Suppose we express the series as

1
X m
X 1
X
k k k
H( )= ak = ak + ak ; (10.90)
k=0 k=0 k=m
where k = m > N; for extremely big integer N . Noting that for large k, the
recursion relation becomes
1
ak+1 = ak ;
k
and one …nds for k = m > N;
1
am+1 = am ;
m
1 1
am+2 = am+1 = am ;
m+1 (m + 1) m
1 1
am+3 = am+2 = am ;
m+2 (m + 2) (m + 1) m
1 1
am+4 = am+3 = am :
m+3 (m + 3) (m + 2) (m + 1) m
that lead to
1
am+k = am
(m + k 1) ::: (m + 2) (m + 1) m
for m = 1, we have
1
a2 = a1 ;
1
1 1
a3 = a2 = a1 ;
2 2 1
1 1
a4 = a3 = a1 ;
3 3 2 1
1 1
a1+k = ak 1 = a1 ;
k k (k 1) (k 2) ::::3 2 1
or
1
a1+k =
a1 :
k!
Now if we rewrite the second term in the series in Eq. (10.90) as
1
X 1
X
k m k
ak = ak+1 ; (10.91)
k=m k=0
using the result above, we …nd

1
X 1
X
k 1
ak = a01 m k
= a01 m
e : (10.92)
k!
k=m k=0
This gives
m
X
k
H( )= ak + a01 m
e (10.93)
k=0
which is a diverging function and is not acceptable. Therefore the series must
terminate for some value of k. Let say the series terminates for some positive
integer, k = nr . This requires for k = nr
ak+1 k+l+1 nr + l + 1
= = =0 (10.94)
ak (k + 1) (2 (l + 1) + k) (nr + 1) (2 (l + 1) + nr )
which leads to
nr + l + 1 = 0: (10.95)
This restricts the values allowed for (i.e. that determines the energy eigen-
value)
= nr + l + 1:
Now if we introduce the principal quantum number n de…ned as
n= = nr + l + 1 (10.96)
and recalling that

r s
m Ze2 mc2 Ze2
= )n= ; (10.97)
2 jEnl j 4 0 ~ 2 jEnl j 4 0 ~c
in terms of the dimensionless …ne structure constant

e2 1
= = : (10.98)
4 0 ~c 137:036
as s
mc2
n=Z : (10.99)
2 jEnl j
we can write
2
mc2 (Z )
jEnl j = : (10.100)
2 n2
Therefore, the energy of the electron in a Hydrogenic atom can be expressed as
2
mc2 (Z )
Enl = jEnl j = : (10.101)
2 n2
The principal quantum number, n; satis…es the following conditions
1. since k = nr > 0; the principal quantum number
nr = n (l + 1) > 0 ) n > l + 1 (10.102)

2. n is a positive integer since we already have shown that l = 0; 1; 2::: and

it is an integer, we note that the principal quantum number must be
n = 1; 2; 3::: (10.103)
The energy eigen functions and the degeneracy of the spectrum: we recall
r
8m jEnl j
= r (10.104)
~2
which can be expressed, in terms of the expression we determined for the energy,
as s
2
4m2 c2 (Z ) 2Z mc r
= r= : (10.105)
~2 n2 ~ n
Using the Bohr radius de…ned as
~
a0 = ; (10.106)
mc
we may write
2Zr
= : (10.107)
a0 n
Then the radial wave function
l =2
Rnl ( ) = e H( ) (10.108)
can be expressed as
l
2Zr Zr 2Zr
Rnl (r) = e a0 n
Hn : (10.109)
a0 n a0 n
where
1
X k
2Zr
Hn ( ) = bk (10.110)
a0 n
k=0
and bk is determined by
bk+1 k+l+1 n
= : (10.111)
bk (k + 1) (2 (l + 1) + k)
The ground state: for the ground state we have n = 1; which means
n = nr + l + 1 = 1 ) kmax = nr = l = 0 (10.112)
and the series

1
X k
2Zr
Hn ( ) = bk (10.113)
a0 n
k=0
becomes
H ( ) = b0 (10.114)
and the radial wave function is given by
Zr
R10 (r) = b0 e a0
: (10.115)
Since for l = 0; m = 0, the angular part of the wave function is just Y00 ( ; ')
and therefore the energy eigen function would be
100 (r; ; ') = R10 (r) Y00 ( ; ') : (10.116)
The spherical Harmonics Ylm ( ; ') are already normalized functions according
to Z 2 Z
2
d' sin ( ) jYlm ( ; ')j d = 1: (10.117)
0 0
Thus, as the eigen function must be normalized, for the radial part we must
have Z 1
2
jRnl (r)j r2 dr = 1: (10.118)
0
For R10 (r), one can then write
Z 1
2Zr
b20 e a0
r2 dr = 1: (10.119)
0
and upon carrying out the integration, one …nds

3
b20 a0 3 Z 2
= 1 ) b0 = 2 : (10.120)
4 Z a0
Then the radial part for n = 1 and l = 0 becomes
3
Z 2
Zr
R10 (r) = 2 exp : (10.121)
a0 a0
We recall from Theo. Phys. I, the spherical Harmonics are determined by the
equation
s
m 2l + 1 (l m)! m
Ylm ( ; ') = ( 1) P (cos ) eim' (10.122)
4 (l + m)! l
where Plm (cos ) are the associated Legendre polynomials given by

m=2 dm
Plm (x) = 1 x2 Pl (x) : (10.123)
dxm
for x = cos : For l = m = 0, we have
r
1
Y00 ( ; ') = : (10.124)
4
so that the energy eigen function for the ground state becomes
r 3
1 Z 2
Zr
100 (r; ; ') = R10 (r) Y00 ( ; ') = 2 exp : (10.125)
4 a0 a0
The …rst excited state: for the …rst excited state, we have n = 2; which
means
n = nr + l + 1 = 2 ) kmax = nr = 0; 1: (10.126)
For n = 2 and kmax = nr = 0; we note that l = 1, and the series
1
X k
2Zr
H (r) = bk (10.127)
a0 n
k=0
becomes
H21 (r) = b0 : (10.128)
On the other hand for and for n = 2 and kmax = nr = 1 we must have, l = 0;
and the series becomes
Zr
H20 (r) = b0 + b1 :
a0
Using the recursion relation
bk+1 k+l+1 n
= : (10.129)
bk (k + 1) (2 (l + 1) + k)
for k = l = 0, we …nd
b1 0+0+1 2 1
= =
b0 (0 + 1) (2 (0 + 1) + 0) 2
so that
Zr
H20 (r) = b0 1 : (10.130)
2a0
This means for the …rst excited state, the radial part of the eigen function
l
2Zr Zr 2Zr
Rnl (r) = e a0 n
Hn (10.131)
a0 n a0 n
leads to two di¤erent radial eigen functions given by
Zr Zr
R20 (r) = b0 1 exp (10.132)
2a0 2a0
and
Zr Zr
R21 (r) = b0 exp : (10.133)
a0 2a0
Applying the normalization condition for the radial function one can show that
3
Z 2
Zr Zr
R20 (r) = 2 1 exp (10.134)
2a0 2a0 2a0
and 3
1 Z 2
Zr Zr
R21 (r) = p exp : (10.135)
3 2a0 a0 2a0
Since for, n = 2; l = 0; and m = 0, the angular part of the wave function is
just Y00 ( ; ') using the radial function R20 (r), the energy eigen function can
be written as
200 (r; ; ') = R20 (r) Y00 ( ; ') : (10.136)
On the other hand for n = 2; l = 1; we have m = 1; 0; 1 which means there are
three di¤erent eigen functions for the angular momentum L ^ 2 i.e. (Y1 1 ; Y10 Y11 ) :
Therefore using the radial function R21 (r), we can write three more energy eigen
functions
21 1 (r; ; ') = R21 (r) Y1 1 ( ; ') ; 210 (r; ; ') = R21 (r) Y10 ( ; ') ;
211 (r; ; ') = R21 (r) Y11 ( ; ') : (10.137)
Totally for the energy eigen state, n = 2,there are four di¤erent states described
by the eigen functions
200 (r; ; ') = R20 (r) Y00 ( ; ') ; 21 1 (r; ; ') = R21 (r) Y1 1 ( ; ')
210 (r; ; ') = R21 (r) Y10 ( ; ') ; 211 (r; ; ') = R21 (r) Y11 ( ; ')
which means this energy level is degenerate and it has four degeneracy.
Degeneracy: in general for a given energy state n, the number of degeneracy
in a hydrogenic atom is given by
lX
max n
X1
(2l + 1) = (2l + 1) = n2 :
l=0 l=0
Part II
Quantum Mechanics II
-PHYS 4390
261
Chapter 11
Time-Independent
Perturbation Theory
There are a few potential for which the Schrödinger equation is exactly solvable
for which the energy eigenvalues and eigenstates can be determined. Computers
can indeed be used if only numerical values are needed for the eigenvalues. Here,
we learn a technique known as perturbation theory to obtain the approximate so-
lution for such kind of problems without using computers. Most of such physical
problems are close to the ones that we did solve, such as harmonic oscillator and
Hydrogenic atoms, we can treat the di¤erence as perturbation. Using perturba-
tion theory, even at the lowest level of approximation, we get insight into how
energies shift and how eigen functions are changed by a change in the potential.
The speci…c topics include: Nondegenerate and degenerate perturbation theory;
application of perturbation theory-the Stark E¤ect in hydrogen atom; applica-
tion of perturbation theory in the real hydrogen atom-relativistic corrections,
relativistic kinetic energy, spin-orbit coupling, corrected energy levels and the
Zeeman e¤ects
11.1 Nondegenerate and degenerate perturba-

tion theory
Suppose we have the solution to the eigenvalue equation for some potential (e.g.
the 1-D harmonic oscillator) describing a given physical system
^0 j
H ni = En0 j ni ; (11.1)
where H^ 0 is the quantum Hamiltonian for the physical system, En0 and j n i
are the energy eigenvalue and eigenstates obtained by solving the eigenvalue
equation, respectively. Moreover, we also know the energy eigenstates form a
complete orthonormal set of vectors
h m j ni = mn : (11.2)
263
264 CHAPTER 11. TIME-INDEPENDENT PERTURBATION THEORY
Let’s say we have made a small change in the potential energy of the system
(perturb it slightly). For example for a harmonic oscillator the unperturbed
potential and the perturbed potential are shown in Fig. [?]. This perturbation
Figure 11.1: Unperturbed and perturbed elastic potential energy.
could be due to, for example, a uniform external electric …eld if the system is
charged. As a result the Hamiltonian of the system will be di¤erent and let this
^ The eigenvalue equation for this perturbed system can then
Hamiltonian be H.
be expressed as
H^ j n i = En j n i ; (11.3)
where En and j n i are the energy eigenvalue and eigenstates obtained for the
perturbed system, respectively. Often obtaining analytical solution to such
eigenvalue equation is hard and in most cases impossible. Perturbation theory
is a systematic procedure for obtaining approximate solutions to such eigenvalue
problems. It is based upon the exact solution obtained for the corresponding
unperturbed system eigenvalue equation. If the eigenstates for the unperturbed
system shows degeneracy we use the degenerate perturbation theory otherwise
we use the nondegenerate perturbation theory. We shall begin with the nonde-
generate perturbation theory.
11.1.1 Nondegenerate perturbation theory

The perturbed system Hamiltonian, H,^ in terms of the corresponding unper-
^
turbed Hamiltonian, H0 ; can be expressed as
^ =H
H ^0 + H
^ 1; (11.4)
where H^ 1 is the term in the Hamiltonian resulting from the perturbation in
the potential energy of the system and for the time being we take it as a
11.1. NONDEGENERATE AND DEGENERATE PERTURBATION THEORY265
^ be the true
small number but later we give it a value one ( = 1) so that H
Hamiltonian of the perturbed system
^ =H
H ^0 + H
^ 1: (11.5)
Using Eq. (11.4), the eigenvalue equation in Eq. (11.3) can be expressed as
^0 + H
H ^1 j ni = En j ni : (11.6)
We recall that the eigenstates for the unperturbed system form a complete set
of orthonormal vectors
X1
j k i h k j = I:
k
Therefore, we can express the eigenstate for the perturbed system, j n i ; as

a linear superposition for the eigenstates for the corresponding unperturbed
eigenstates, j k i ;
1
X
j ni = h k j ni j k i (11.7)
k
Now let’s isolate the term k = n from the summation so that we can write
2 3
1
X
j n i = N ( ) 4Cnn ( ) j n i + Cnk ( ) j k i5 : (11.8)
k6=n
The factor N ( ) is determined from the othonormalization condition
h m j ni = mn : (11.9)
and therefore we have the freedom to chose the phase for j n i ; (i.e. N ( )) : We
can then chose this phase so that it can set Cnn ( ) = 1 and we write Eq. (11.8)
as 2 3
X1
j n i = N ( ) 4j n i + Cnk ( ) j k i5 : (11.10)
k6=n
Note that since this eigenstate must reduce to j ni for the unperturbed system
as ! 0, we must have
N (0) = 1 and Cnk (0) = 0 (11.11)
Taking this into consideration, we can express the expansion coe¢ cients Cnk ( )
for k 6= n as
(1) (2) (3)
Cnk ( ) = Cnk + 2 Cnk + 3 Cnk + ::: (11.12)
so that one …nds Cnk (0) = 0: Based on the same argument, since we are expect-
ing the energy eigenvalue for the perturbed system En must reduce to the energy
of the unperturbed system En0 in the absence of perturbation (i.e. ! 0), we

may express
En = En0 + En(1) + 2 En(2) + 3 En(3) + ::: (11.13)
(1) (2) (3)
where En ; En ; En ... are 1st, 2nd, 3rd...order corrections due to the per-
turbing Hamiltonian H ^1
(i) First order perturbation theory: In the …rst order perturbation theory we
keep the terms in Eqs. (11.12) and (11.13) up to the …rst order of ; so that
(1)
Cnk ( ) = Cnk (11.14)
and
En = En0 + En(1) : (11.15)
The energy eigenstate for the perturbed system becomes
2 3
X1
(1)
j n i = N ( ) 4j n i + Cnk j k i5 : (11.16)
k6=n
Using Eqs.(11.15) and (11.16), the eigenvalue equation for the perturbed system
in Eq. (??) can be expressed as
2 3
X1
^ 1 N ( ) 4j n i + (1)
^0 + H
H Cnk j k i5 = En0 + En(1) N ( ) (11.17)
k6=n
2 3
1
X
4j (1) 5:
ni + Cnk j ki (11.18)
k6=n

1
X 1
X
^0 j (1) ^ ^ 2 (1) ^
H ni + Cnk H 0j k i + H1 j ni + Cnk H 1j ki = En0 j ni
k6=n k6=n
1
X 1
X
(1) 2 (1)
+ Cnk En0 j ki + En(1) j ni + Cnk En(1) j ki : (11.19)
k6=n k6=n
Using the results for the energy eigenvalue equation for the unperturbed system
in Eq. (??) and noting that in the …rst order perturbation theory we keep only
the terms up to …rst order in ; the above expression reduces to
1
X 1
X
(1) ^ (1)
Cnk Ek0 j k i + H1 j ni = Cnk En0 j ki + En(1) j ni
k6=n k6=n
1
X (1) ^1 j
) En(1) j ni = Cnk Ek0 En0 j ki +H ni (11.20)
k6=n
Multiplying Eq. (11.20) by h nj ; we …nd

1
X (1) ^ j
En(1) h n j ni = Cnk Ek0 En0 h n j ki +h n j H1 ni (11.21)
k6=n
so that using Eq. (??), the expression for the …rst order correction for the
energy can be expressed as
1
X (1) ^ j ^ j
En(1) = Cnk Ek0 En0 nk +h n j H1 ni ) En(1) = h n j H1 ni ; (11.22)
k6=n
Using the completeness relation for position eigenstates

Z
dx jxi hxj = I
twice in Eq. (11.22), we may write

Z Z
(1) ^
En = h n j dx jxi hxj H1 dx0 jx0 i hx0 j j ni : (11.23)
which can be rewritten as

Z Z
En(1) = dx dx0 h nj
^ 1 jx0 i hx0 j
xi hxj H ni : (11.24)
For a perturbation that has the form

^ 1 = V (^
H x) (11.25)
we may write
^ 1 jx0 i = V (x0 ) hxj x0 i = V (x0 ) (x
hxj H x0 ) (11.26)
so that
Z Z
En(1) = dx dx0 h nj xi V (x0 ) (x x0 ) hx0 j ni : (11.27)
or Z Z
En(1) = dx n (x) V (x) n (x) : (11.28)
where we have applied the property of the Dirac-delta function

Z
dx0 f (x0 ) (x x0 ) = f (x) ; (11.29)
and the Dirac notation
n (x) = hx j ni ; n (x) = h nj xi : (11.30)

We now proceed to …nd the eigenstates. To this end, we multiply Eq. (11.20)
by h m j
1
X (1) ^ j
En(1) h m j ni = Cnk Ek0 En0 h m j ki +h m j H1 ni (11.31)
k6=n
so that
1
X (1) ^ j
En(1) mk = Cnk Ek0 En0 mk +h m j H1 ni (11.32)
k6=n
For m 6= n; we …nd
1
X (1) ^ j
Cnk Ek0 En0 mk = h m j H1 ni : (11.33)
k6=n
We know m can be the same as k and still be, k 6= n; ; thus the above equation
can be expressed as
(1)
Cnm 0
Em En0 = h m j H1
^ j ni (11.34)
so that
^ 1 j ni
h mj H
(1)
Cnm = : (11.35)
(Em En0 )
0
In summary in the …rst order perturbation theory we can determine the energy
and the eigenstates for the perturbed system using
En = En0 + En(1) = En0 + h n j H1

^ j ni (11.36)
and 2 3
1
X ^ 1 j ni
h kj H
j ni = N 4j ni j ki
5: (11.37)
(Ek0 En0 )
k6=n
where N is a constant that should be determined from the condition
h n j ni = 1: (11.38)
(i) Second order perturbation theory: In the second order perturbation theory
we keep the terms in Eqs. (11.12) and (11.13) up to the 2nd order of ; so that
(1) 2 (2)
Cnk ( ) = Cnk + Cnk (11.39)
and
2
En = En0 + En(1) + En(2) (11.40)
2 3
1
X (1) (2)
j n i = N ( ) 4j n i + Cnk + 2 Cnk j ki
5: (11.41)
k6=n
Using Eqs.(11.39) and (11.40), the eigenvalue equation for the unperturbed
system in Eq. (??) can be expressed as
2 3
1
X
^ 1 N ( ) 4j n i + (1) (2)
H^0 + H Cnk + + 2 Cnk j k i5 (11.42)
k6=n
2 3
1
X (1) (2)
= En0 + En(1) + 2
En(2) N ( ) 4j ni + Cnk + + 2
Cnk j ki
5:
k6=n
(11.43)
Using the results for the energy eigenvalue equation for the unperturbed system
in Eq. (??) and by keeping the terms up to 2nd order in ; it can be shown that
results in
2
X1 h ^
n j H1 j k i
(2)
En = (11.44)
En0 Ek0
k6=n
and P1
(1) (1) (1) ^ j
(2)
Cnm En k6=n Cnk h m j H1 ki
Cnm = 0
: (11.45)
(Em En0 )
N.B. Following the same procedure we followed in …rst order perturbation theory
you are expected to drive Eqs. (11.44) and (11.45) in your …rst homework
assignment.
Example 1 Consider a charged particle in a simple Harmonic oscillator, for

which
2
H^ 0 = p^ + 1 m! 2 x2 (11.46)
2m 2
~ = Ex
subject to a constant electric …eld along the positive x-axis, E ^, as
shown in Fig. 11.2 so that
2
^ = p^ + 1 m! 2 x2
H qEx (11.47)
2m 2
where
^ 1 = qEx:
H (11.48)
Calculate the energy shift for the nth level to the …rst and second order
in (qE).
Solution: Using the results we determined for a …rst order perturbation
En(1) = h n j H1
^ j ni ; (11.49)
and using the the eigenstates j n i = jni and the ladder operators
r r
1 2~ y ^ qE 2~
x
^= a
^+a ^ ) H1 = a
^+a^y : (11.50)
2 m! 2 m!
Figure 11.2: A charged Harmonic oscillator in a uniform electric …eld.
and recalling that

p p
a
^ jni = n jn ^y jni =
1i ; a n + 1 jn + 1i (11.51)
we have
r
En(1) = h n j H ^ 1 jni = qE
^ 1 j n i = hnj H 2~
hnj a ^y jni
^ jni + hnj a
2 m!
r
qE 2~ p p
= n hnj n 1i + n + 1 hnj n + 1i ) En(1) = 0 (11.52)
2 m!
where we used the orhonormality of the energy eigen functions for the
unperturbed Harmonic oscillator. This shows that there is no correction
in energy if we limited to the …rst order perturbation theory. So we need
to use the second order perturbation correction. We recall that for the
second order correction, we have
2
1 h
X n j H1
^ j ki
En(2) = (11.53)
En0 Ek0
k6=n

q 2
qE 2~
1
X 2 m! hnj a ^y jki
^ jki + hnj a
En(2) =
En0 Ek0
k6=n
p p 2
qE
2 1
2~ X k hnj k 1i + k + 1 hnj k + 1i
= : (11.54)
2 m! En0 Ek0
k6=n
Once again using the orthonormality condition for the energy eigen states,
we have
p p 2
qE
2
2~ X1 k n;k 1 + k + 1 n;k+1
En(2) = ; (11.55)
2 m! En0 Ek0
k6=n
so that using
hnj k 1i = n;k 1 )k 1 = n ) k = n + 1;
hnj k + 1i = n;k+1 )k+1=n)k =n 1
one …nds
p 2 p 2
!
2
qE 2~ n+1 n 1
En(2) = 0 + 0
2 m! 0
En En+1 En En0 1
2
qE 2~ n+1 n 1
= 0 + 0 : (11.56)
2 m! En0 En+1 En En0 1
For the unpertubed harmonic oscillator using

1
En0 = ~! n + )
2
1 1
En0 0
En+1 = ~! n + ~! n + +1 = ~!;
2 2
1 1
En0 En0 1 = ~! n + ~! n + 1 = ~! (11.57)
2 2
we …nd
q2 E 2
En(2) = : (11.58)
m! 2
11.1.2 Degenerate perturbation theory

As one can see from Eqs. (11.35) and (11.44), when there are two or more
eigenstates of the unperturbed system have the same eigenvalue (degenerate
states), we will be in trouble since both Eqs. (11.35) and (11.44) diverge. In
such cases the perturbation theory we developed in the previous section can
not be directly applied unless somehow we remove the degeneracy …rst. If one
can remove the degeneracy, then the nondegenerate perturbation theory can
directly be used. For example, consider an unperturbed system with three
energy eigenvalues two of which are degenerate. Using matrix representation,
we may write the unperturbed Hamiltonian
2 0 3
E 0 0
H0 = 4 0 E 0 0 5 ; (11.59)
0 0 E30
where we used
E10 = E20 = E 0 : (11.60)
If the perturbed part of the Hamiltonian, using matrices, can be expressed as
2 3
h11 h12 h13
H1 = 4 h21 h22 h23 5 ; (11.61)
h31 h32 h33
where
hij = hji (11.62)
since the Hamiltonian is Hermitian. We recall that a Hermitian matrix, H; can
be diagonalized by a unitary transformation
HD = U HU y : (11.63)
0
Consider a unitary matrix, U ,
u11 u12
U0 = : (11.64)
u21 u22
that diagonalizes the 2 2 matrix
h11 h12
H10 = ; (11.65)
h21 h22
such that
0 w+ 0
HD = U H10 U y = : (11.66)
0 w
Then for the matrix 2 3
u11 u12 0
U = 4 u21 u22 0 5: (11.67)
0 0 1
one can write
2 32 32 3y
u11 u12 0 h11 h12 h13 u11 u12 0
4 u21 u22 0 5 4 h21 h22 h23 5 4 u21 u22 0 5
0 0 1 h31 h32 h33 0 0 1
2 3
w+ 0 h13
=4 0 w h23 5 ; (11.68)
h31 h32 h33
where w are factors that we will use to eliminate the degeneracy and are
determined by solving the eigenvalue equation
h11 h12 a1 a1
=w (11.69)
h21 h22 a2 a2
which leads to
s
2
h11 + h22 h11 h22
w = h12 h21 : (11.70)
2 2
Noting that
2 32 0 32 3y
u11 u12 0 E 0 0 u11 u12 0
4 u21 u22 0 5 4 0 E 0 0 5 4 u21 u22 0 5
0 0 1 0 0 E30 0 0 1
2 0 3
E 0 0
= 4 0 E0 0 5 ; (11.71)
0 0 E30
we may write the matrix for the total Hamiltonian

2 0 3 2 3
E 0 0 w+ 0 h13
H = H0 + H1 = 4 0 E 0 0 5 + 4 0 w h23 5
0 0 E30 h31 h32 h33
2 0 3 2 3
E + w+ 0 0 0 0 h13
)H=4 0 E0 + w 0 5+4 0 0 h23 5 : (11.72)
0 0 E30 h31 h32 h33
Note that in this expression we have removed the degeneracy in the unperturbed
part of the Hamiltonian. This means we can apply the relations derived for both
the …rst and second order nondegenerate perturbation theory.
We have seen how we can apply the nondegenerate perturbation relations
can be used after removing the degeneracy. We now develop a general relation
that integrates the degeneracy. Suppose we form a set of mk degenerate states
that have the same energy eigenvalue Ek0
E E E E E
(i) (1) (2) (3) (mk )
k = k ; k ; k ::: k :
These degenerate eigenstates form an orthonormal inside as well as outside this

set, that means D E
(i) j
k0 = kk ij : (11.73)
0
k
Following a similar procedure we used for the nondegenerate case, the complete-
ness relation
1
X
j k i h k j = I;
k
which we may write for degenerate states

mk
1 X
X ED
(i) (i)
k k = I;
k=1 i=1
one can express the eigenstate for the perturbed Hamiltonian

^ =H
H ^0 + H
^ 1; (11.74)
as
mk D
1 X
X E
(i) (i)
j ni = k ni k (11.75)
k=1 i=1
By isolating all the degenerate eigenstates with energy eigenvalue En0 ; again
following a similar argument we made for the nondegenerate case, one can write
2 3
mn
X E X1 mk
X E
(1) (2) (i)
j ni = N ( ) 4 i
(i)
n + C + 2 C ::: nk i + :::5
nk k
i=1 k6=n i=1
(11.76)
with corresponding eigenvalues

2 3
En = En0 + En(1) + En(2) + En(3) + ::: (11.77)
Substituting these two relations in the eigenvalue equation

^j
H ni = En j ni ; (11.78)
we have
2 2 33
Xmn E 1
X mk
X E
^0 + H
^1 4N ( ) 4 (i) (1) 2 (2) (i) 55
H i n + Cnk + Cnk ::: i k
i=1 k6=n i=1
" mn
X E
2 3 (i)
= En0 + En(1) + En(2) + En(3) + ::: N( ) i n
i=1
3
1
X mk
X E
(1) 2 (2) (i) 5;
+ Cnk + Cnk ::: i k (11.79)
k6=n i=1
For the 1st order approximation (dropping all the terms involving n
, for n = 2);
we …nd for the left side of Eq. (11.79)
2 2 33
mn
X E X1 mk
X E
^0 + H ^ 1 4N ( ) 4 (i) (1) (i) 55
H i n + C i nk k
i=1 k6=n i=1
2 3
Xmn E 1
X mk
X E mn
X E
(1) (i)
= N ( )4 ^
i H0
(i)
n + Cnk ^
i H0 k + ^
i H1
(i) 5
n
i=1 k6=n i=1 i=1
(11.80)
0 1
mn
X E 1
X mk
X E mn
X E
(1) (i)
= N ( ) @En0 i
(i)
n + Cnk 0
i Ek k + ^
i H1
(i) A
n ;
i=1 k6=n i=1 i=1
(11.81)
and for the right side

" mn
X E
2 3 (i)
En0 + En(1) + En(2) + En(3) + ::: N( ) i n
i=1
3
1
X mk
X E
(1) 2 (2) (i) 5=
+ Cnk + Cnk ::: i k (11.82)
k6=n i=1
2 3
mn
X E 1
X mk
X E mn
X E
(1) (i)
N ( ) 4En0 i
(i)
n + En0 Cnk i k + En(1) i
(i) 5
n :
i=1 k6=n i=1 i=1
(11.83)
There follows that

mn
X E 1
X mk
X E mn
X E
0 (i) (1) 0 (i) ^ (i)
i En n + Cnk i Ek k + i H1 n
i=1 k6=n i=1 i=1
mn
X E 1
X mk
X E mn
X E
0 (i) (1) 0 (i) (1) (i)
= i En n + Cnk i En k + i En n ; (11.84)
i=1 k6=n i=1 i=1

1
X mk
X E mn
X E 1
X mk
X E
(1) 0 (i) ^ (i) (1) 0 (i)
Cnk i Ek k + i H1 n = Cnk i En k
k6=n i=1 i=1 k6=n i=1
mn
X E
(1) (i)
+ i En n ; (11.85)
i=1
D
(j)
Multiplying the above expression with n from the left, we have
1
X mk
X D E mn
X D E
(1) 0 (j) (i) (j) ^1 (i)
Cnk i Ek n k + i n H n
k6=n i=1 i=1
1
X mk
X D E mn
X D E
(1) 0 (j) (i) (1) (j) (i)
= Cnk i En n k + i En n n ; (11.86)
k6=n i=1 i=1
and using the orthonormality requirement for the energy eigen functions, in Eq.
(11.73),
1
X mk
X mn
X D E
(1) 0 (j) ^1 (i)
Cnk i Ek nk ji + i n H n
k6=n i=1 i=1
1
X mk
X mn
X
(1) 0 (1)
= Cnk i En nk ji + i En ji
k6=n i=1 i=1
1
X mn
X D E 1
X
(1) 0 (j) ^1 (i) (1) 0 (1)
) Cnk j Ek nk + i n H n = Cnk j En nk + j En
k6=n i=1 k6=n
(11.87)
Since k 6= n; we have nk = 0 that leads to
mn
X D E
i
(j)
n
^1
H (i)
n = (1)
j En : (11.88)
i=1
Eq. (11.88) is a …nite dimensional eigenvalue equation. For example, for a

threefold degeneracy, we have
3
X D E
i
(j)
n
^1
H (i)
n = (1)
j En (11.89)
i=1
with j = 1; 2; 3: The resulting equation for these values of j are

D E D E D E
(1) ^ ^ 1 (2) ^ 1 (3)
1 n H1 (1)n + 2 (1) n H n + 3 (1)n H n = (1)
1 En
D E D E D E
(2) ^ ^ 1 (2) ^ 1 (3)
1 n H1 (1)n + 2 (2) n H n + 3 (2)n H n = (1)
2 En
D E D E D E
(3) ^ ^ 1 (2) ^ 1 (3)
1 n H1 (1)n + 2 (3) n H n + 3 (3)n H n = En(1)
3(11.90)
which we can put, using matrices, in the form

2 32 3 2 3
h11 h12 h13 1 1
4 h21 h22 h23 5 4 2 5 = En(1) 4 2
5; (11.91)
h31 h32 h33 3 3
where D E
hji = (j) ^1
H (i)
: (11.92)
n n
(1)
The En and i can be determined by solving Eq. (11.91) and the condition
for orthonormalization of the linear superposition of the degenerate states
X E X
(i) 2
j i= i n )h j i=1) j i j = 1: (11.93)
i i
Here we are not interested in …nding i since we limit our interest in the energy
eigenvalues only.
11.2 PT application I - The Stark e¤ ect

Next we will see the application of perturbation theory for a real physical sys-
tems. In particular we will consider a Hydrogenic atom in a uniform external
electric …eld. But …rst we will review the Hydrogenic atom eigenvalue problem
from last semester.
11.2.1 Hyrdogenic atom-review

The Central Potential : when the potential energy depends only on the variable,
r;in spherical coordinates, the potential is said to be central and we can write
V (r; ; ') = V (r) : (11.94)
For such potential the eigenvalue equation (time independent Schrödinger Equa-
tion) in spherical coordinates can be expressed as
" #
~2 @ 2 2 @ ^2
L
+ (r; ; ')+V (r) (r; ; ') = E (r; ; ') ; (11.95)
2m @r2 r @r ~2 r2
11.2. PT APPLICATION I - THE STARK EFFECT 277
^ is the angular momentum operator given by

where L
^2 = @2 @ 1 @2
L ~2 + cot ( ) + : (11.96)
@ 2 @ sin2 ( ) @'2
For a central potential, the Hamiltonian

" #
~2 @ 2 2 @ ^2
L
^
H0 = + + V (r) (11.97)
2m @r 2 r @r ~2 r 2
^2,
commutes with the total angular momentum operator, L
h i
^ 0; L
H ^ 2 = 0: (11.98)
We know that for such commuting operators, one can determined a simultaneous
^ 2 , which is
eigen function. Since we already know the eigenvalue equation for L
given by
^ 2 Ylm ( ; ') = ~2 l (l + 1) Ylm ( ; ') ;
L (11.99)
where Ylm ( ; ') are the spherical Harmonics, for the energy eigenvalue equation
^ 0 (r; ; ') = E 0 (r; ; ')
H (11.100)
n
one can express the energy eigen functions as
(r; ; ') = Rnl (r) Ylm ( ; ') (11.101)

^ and L
which is a simultaneous eigen function to H ^ 2 : Substituting this into the
energy eigenvalue equation, we can write
^ 0 Rnl (r) Ylm ( ; ') = Enl
H 0
Rnl (r) Ylm ( ; ') : (11.102)
In a hydrogenic atom there are Z protons in the nucleus and an electron located
at a distance r from the nucleus. This electron experiences an attractive elec-
tostatic force and the potential energy due to this interaction is central given
by
1 Ze2
V (r) = :
4 0 r
For this potential energy, we have determined the energy of the electron is given
by
2
mc2 (Z )
Enl = ; (11.103)
2 n2
and the radial part of the eigen function
l
2Zr Zr 2Zr
Rnl (r) = e a0 n
Hn ; (11.104)
a0 n a0 n
where
n = 1; 2; 3::::; l = 0; 1; 2:::n 1; m = l; l + 1:::0:::l 1; l: (11.105)
We recall from Theo Phys. I, the spherical Harmonics, Ylm ( ; ') ; are given by
s
m 2l + 1 (l m)! m
Ylm ( ; ') = ( 1) P (cos ) gm (') ;
4 (l + m)! l
m=2 dm
Plm (x) Plm (x) = 1 x2 Pl (x) ; gm (') = eim' : (11.106)
dxm
wherePl (x) is the Legendry polynomials given by
1 dl l
Pl (x) = x2 1 ; (11.107)
2l l! dxl
with x = cos ( ) and the orthogonality relation
2
hPn (x)j Pl (x)i = l;n : For jxj 1: (11.108)
2l + 1
The Spherical Harmonics form an orthonormal set of functions satisfying the
relation
Z Z 2
hYlm ( ; ')j Yl0 m0 ( ; ')i = Ylm ( ; ') Yl0 m0 ( ; ') sin d d' := ll0 mm0 :
=0 '=0
(11.109)
Using the expressions above or a Mathematical programing software (such as
Mathematica), for l = 0; m = 0 and l = 2; m = 1; 0; 1; one …nds
1
Y00 ( ; ') = p ;
2
r r
1 3
i' 1 3
Y1 1 ( ; ') = e sin ( ) ; Y10 ( ; ') = cos ( ) ;
2 2 2
r r
1 2i' 15 2 1 i' 15
Y2 2 ( ; ') = e sin ( ) ; Y2 1 ( ; ') = e sin ( ) cos ( ) ;
4 2 2 2
r
1 i' 5
Y20 ( ; ') = e 3 cos2 ( ) 1 : (11.110)
4
The ground state: for the ground state we have n = 1; which means and l = 0
and m = 0
3
Z 2
Zr 1
R10 (r) = 2 exp ; Y00 ( ; ') = p : (11.111)
a0 a0 2
and the energy eigen function
3
1 Z 2
Zr
100 (r; ; ') = R10 (r) Y00 ( ; ') = p exp : (11.112)
a0 a0
The …rst excited state: for the 1st excited state, we have n = 2; which means
0; m = 0;
l= (11.113)
1; m = 1; 0; 1:
The radial part of the energy eigen function, Rnl (r) for n = 2; l = 0; and
n = 2; l = 1; are
3
Z 2
Zr Zr
R20 (r) = 2 1 exp ;
2a0 2a0 2a0
3
1 Z 2
Zr Zr
R21 (r) = p exp : (11.114)
3 2a0 a0 2a0
The energy eigen functions can then be written as

3
1 Z 2
Zr Zr
200 (r; ; ') = R20 (r) Y00 ( ; ') = p 1 exp
2a0 2a0 2a0
(11.115)
and
r 3
1 1 Z 2
Zr Zr i'
21 1 (r; ; ') = R21 (r) Y1 1 ( ; ') = exp e sin ( ) ;
2 2 2a0 a0 2a0
r 3
1 1 Z 2 Zr Zr
210 (r; ; ') = R21 (r) Y10 ( ; ') = exp cos ( ) ;
2 2a0 a0 2a0
r 3
1 1 Z 2
Zr Zr i'
211 (r; ; ') = R21 (r) Y11 ( ; ') = exp e sin ( ) :
2 2 2a0 a0 2a0
(11.116)
These four eigen functions which belong to the same energy eigen value, clearly,
show that the energy eigenvalue, En (n = 2) is four times degenerate. In general,
for a given energy state n, the number of degeneracy in a hydrogenic atom is
given by
lX
max n
X1
(2l + 1) = (2l + 1) = n2 (11.117)
l=0 l=0
11.2.2 Stark E¤ ect in a Hyrdogenic atom

The Stark e¤ ect is generally the shifting and splitting of the energy levels in
atoms or molecules when the atoms or molecules are exposed to an external
electric …eld.
The e¤ ect is named after the German physicist Johannes Stark, who dis-
covered it in 1913. It was independently discovered in the same year by the
Italian physicist Antonino Lo Surdo, and in Italy it is thus sometimes called the
Stark–Lo Surdo e¤ ect. The discovery of this e¤ ect contributed importantly to
the development of quantum theory and was rewarded with the Nobel Prize in
Physics for Johannes Stark in the year 1919.[From Wikipedia]
Here we shall see Stark e¤ect by applying Perturbation theory in a Hydro-
genic atoms. To this end, consider a Hydrogenic atom placed in a uniform
~ = E z^ axis as shown in Fig.11.3.
electric …eld directed along the positive z , E
Figure 11.3: A Hydrogenic atom in a uniform electric …eld.
Neglecting the displacement of the heavy nucleus (the Z protons due to its heavy
mass), the additional energy resulting from the interaction of the electron with
external …eld can be considered as a small perturbation. This perturbing energy,
in spherical coordinates, is given by
^ 1 = eE
H ~ ~r = eEz = eEr cos ( ) : (11.118)
Stark E¤ ect for the ground state: The ground state is nondegenerate and we
can use the nondegenerate perturbation theory to determine the energy shift.
Using the relation in Eq. (11.88) one can write
(1) ^ j
E1 =h 100 j H1 100 i =h 100 j eEr cos ( )j 100 i (11.119)
which we may express as
Z1 Z 2 Z
(1) 2 2 2
E1 = drr jR10 (r)j d' cos ( ) sin ( ) jY00 ( ; ')j d (11.120)
0 0
0
so that using
1
Y00 ( ; ') = p (11.121)
2
one can easily …nd
Z1 2 Z
(1) 2 1
E1 = drr2 jR10 (r)j (2 ) p cos ( ) sin ( ) d = 0:
2 0
0
Since we found no correction to the …rst order, we must go to the second order.
Using the relations we derived for the second order nondegenerate perturbation
theory, Eq. (11.44) we may write
2
1 h
1 X
X nlm j H1
^ j 100 i
(2)
E1 = (11.122)
E10 En0
n6=1 lm
HW: Determine the result for Eqs. (11.122).

Stark E¤ ect for the …rst excited state (n=2): We recall that the …rst excited
state is fourfold degenerate. This is because for n = 2, we have l = 0; 1, and
for l = 1, we have m = 1; 0; 1: This would lead to the following degenerate
eigenstates for the unperturbed system
200 (r; ; ') = R20 (r) Y00 ( ; ') ;

21 1 (r; ; ') = R21 (r) Y1 1 ( ; ') ; 210 (r; ; ') = R21 (r) Y10 ( ; ') ;
211 (r; ; ') = R21 (r) Y11 ( ; ') ; (11.123)
where
r
1 1 3
Y00 ( ; ') = p ; Y10 ( ; ') = cos ( ) ;
2 2
r r
1 i' 3 1 i' 3
Y1 1 ( ; ') = e sin ( ) ; Y11 ( ; ') = e sin ( ) ; (11.124)
2 2 2 2
The relation for the 1st order energy shift, for degenerate states (Eq. (11.88))
4
X D E
i
(j)
n
^1
H (i)
n = (1)
j En : (11.125)
i=1
gives 2 32 3 2 3
h11 h12 h13 h14 1 1
6 h21 h22 h23 h24 7 6 7 6 7
6 76 2 7 = E (1) 6 2 7 (11.126)
4 h31 h32 h33 h3 5 4 3 5 2 4
3 5
h41 h42 h43 h44 4 4
where
D E D E D E
(j) ^1 (i) (j) (i) (j) (i)
hji = 2 H 2 = eE 2 z 2 = eE 2 r cos ( ) 2 (11.127)
in which
(1)
2 = 200 (r; ; ') = R20 (r) Y00 ( ; ') ;
(2)
2 = 210 (r; ; ') = R21 (r) Y10 ( ; ') ;
(3)
2 = 211 (r; ; ') = R21 (r) Y11 ( ; ') ;
(4)
2 = 21 1 (r; ; ') = R21 (r) Y1 1 ( ; ') ; (11.128)
The matrix elements in Eq. (11.126) are determined by evaluating the integrals
h nl0 m0 j z
j nlm i = h nl0 m0 j r cos ( ) j nlm i (11.129)
Z1 Z 2 Z
= drr3 Rnl0 (r) Rnl (r) d' cos ( ) sin ( ) Yl0 m0 ( ; ') Ylm ( ; ') d :
0 0
0
We substitute these values in to Eq. (11.128)

2 3
h 200 j z j 200 i h 200 j z j 210 i h 200 j z j 211 i h 200 j z 21 1
6 h 210 j z j 200 i h j z j i h 210 j z j 211 i h 210 j z
7
eE 6
4 h 211 j z j 200 i
210 210 21 1 7
5
h 211 j z j 210 i h 211 j z j 211 i h 211 j z 21 1
21 1 z j 200 i 21 1 z j 210 i 21 1 z j 211 i 21 1 z 21 1
(11.130)
2 3 2 3
1 1
6 7 6 7
6 2 7 = E (1) 6 2 7
4 3
5 2 4
3 5
4 4
and determine the eigenvalues and eigenvectores. Solving the eigenvalue prob-
lem for a 4 4 matrix is not fun. So commonly we exploit the symmetry of the
problem in hand when we deal with application of perturbation theory. We look
for the following two properties to exploit symmetry in simplifying the problem.
(i) Commutation: check for the operators associated with the degeneracy
commutes with the perturbing Hamiltonian. In our case the degeneracy is due
to the di¤erent values for the quantum numbers l and m. The quantum number,
m, is associated with the operator L ^ z which commutes with position operator
for the z-component, z^ (that the perturbing Hamiltonian, H ^ 1 depends on)
h i h i
H^ 1; L
^ z = eE z^; L^ z = 0 ) z^L
^z = L
^ z z^ (11.131)
Noting that
^z j
L nlm i = m~ j nlm i
and
h i h i
h nl0 m0 j H^ 1; L
^z j nlm i = 0 ) eE h nl0 m0 j
^z
z^L ^ z z^ j
L nlm i =0
) eE (m0 m) h nl0 m0 j z j nlm i =0 (11.132)
For m0 = m, the above expression becomes zero independent of the value for
h nl0 m0 j z j nlm i. But for m0 6= m; we must have
h nl0 m0 j r cos ( )j nlm i = 0: (11.133)
There follows that
h 200 j r cos ( )j 211 i =h 200 j r cos ( ) 21 1 =h 210 j r cos ( )j 211 i (11.134)

=h 210 j r cos ( ) 21 1 =h 211 j z 21 1 =0
along with the complex conjugate of these matrix elements,
h 211 j r cos ( )j 200 i = 21 1 r cos ( ) j 200 i =h 211 j r cos ( )j 210 i (11.135)

= 21 1 r cos ( ) j 210 i = 21 1 zj 211 i =0
(ii) Parity: For the diagonal elements, we have

Z1 Z 2 Z
2 2
h nl0 m0 j r cos ( ) j nlm i = drr3 jRnl (r)j d' cos ( ) sin ( ) jYlm ( ; ')j d
0 0
0
(11.136)
so that using
s 2
2 m 2l + 1 (l m)! m
jYlm ( ; ')j = ( 1) P (cos ) gm (')
4 (l + m)! l
2l + 1 (l m)! m 2
= [P (cos )] (11.137)
4 (l + m)! l
we have
2
r 2
1
2 2 1 3
jY00 ( ; ')j = p ; jY10 ( ; ')j = cos2 ( ) ;
2 2
r 2
2 1 3 2
jY1 1 ( ; ')j = sin2 ( ) = jY11 ( ; ')j ; (11.138)
2 2
which are all even functions which lead to

Z
2
cos ( ) sin ( ) jYlm ( ; ')j d = 0 (11.139)
0
since the integrand would be an odd function of : This leads to
h 200 j r cos ( )j 200 i =h 210 j r cos ( )j 210 i = 21 1 r cos ( ) 21 1

(11.140)
=h 211 j r cos ( )j 211 i = 0:
Now using the results in Eqs.(11.134), (11.135) and (11.140), we may write Eq.
(11.130) as
h 200 j r cos ( )j 211 i =h 200 j r cos ( ) 21 1 =h 210 j r cos ( )j 211 i (11.141)

=h 210 j r cos ( ) 21 1 =0
along with the complex conjugate of these matrix elements,
h 211 j r cos ( )j 200 i = 21 1 r cos ( ) j 200 i =h 211 j r cos ( )j 210 i

= 21 1 r cos ( ) j 210 i =0 (11.142)
2 32 3 2 3
0 h 200 j z j 210 i 0 0 1 1
6 h 210 j z j 200 i 0 0 0 7 6 7 6 7
eE 6
4
76 2 7 = E (1) 6 2 7 (11.143)
0 0 0 0 54 3
5 2 4
3
5
0 0 0 0 4 4
which we may reduce to a 2 2 matrix
0 h 200 j z j 210 i 1 (1) 1

eE = E2 (11.144)
h 210 j z j 200 i 0 2 2
or
0 h12 1 (1) 1
= E2 ; (11.145)
h21 0 2 2
where
Z1
h12 = h21 = h 200 j z j 210 i = eE drr3 R20 (r) R21 (r)
0
Z 2 Z
d' cos ( ) sin ( ) Y00 ( ; ') Y10 ( ; ') d : (11.146)
0 0
Using
3
Z 2
Zr Zr
R20 (r) = 2 1 exp ;
2a0 2a0 2a0
3
1 Zr Z 2
Zr
R21 (r) = p exp ;
3 2a0
2a0 a0
r
1 1 3
Y00 ( ; ') = p ; Y10 ( ; ') = cos ( ) ; (11.147)
2 2
we may have
3Z
1
2 Z Zr Zr Zr
h12 = h21 = eE p drr3 1 exp
3 2a0 a0 2a0 a0
0
p Z 2 Z
3
d' cos2 ( ) sin ( ) d (11.148)
4 0 0
3Z Z
1
Z Zr4 Zr Zr
= eE dr 1 exp cos2 ( ) sin ( ) d
2a0 a0 2a0 a0 0
0
(11.149)
Using Mathematica, we …nd
so that
Z3 36a40 2 3a0 eE
h12 = h21 = eE = (11.150)
8a30 Z4 3 Z
The solution to the eigenvalue equation in Eq. (11.145) is determined as follows
(1)
E2 h12
det (1) =0 (11.151)
h21 E2
which gives
(1)
p 3a0 eE
E2 = h12 h21 =
Z
The corresponding eigenvectors can be determine by substituting these values
into Eq. (11.145) and solving 1 and 2 , which we found to be
E 1 3a0 eE E 1 3a0 eE
(1) 1 (1) (1) 1 (1)
E2+ = p , E2+ = ; E2 =p , E2 =
2 1 Z 2 1 Z
In terms of the ket vectors jn; l; ni we may write
E 1 3a0 eE
(1) (1)
E2+ = p (j2; 0; 0i + j2; 1; 0i) for E2+ = (11.152)
2 Z
and E
(1) 1 (1) 3a0 eE
E2 = p (j2; 0; 0i j2; 1; 0i) for E2 = (11.153)
2 Z
The results in Eqs. (11.152) and (11.153) show that while the states j2; 1; 1i
and j2; 1; 1i remain degenerate, the states j2; 0; 0i and j2; 1; 0i will no longer
remain degenerate due to the electric …eld (see the …gure below).We reduced
Figure 11.4: Energy splitting in a Hydrogenic atom due to applied uniform

external electric …eld.
the four by four matrix into a two by two matrix and as a result of that it may
misleadingly appears there are only two eigenvalues
(1)
p 3a0 eE
E2 = h12 h21 = : (11.154)
Z
However note that there are two degenerate eigenvalues,
(1)
E2 =0 (11.155)
as the matrix is a 4 4, matrix. Because of that we see three energy levels

shown in Fig.
11.3 PT application II -the real Hydrogenic atom

Up to this point in our study of Hydrogenic atoms we did not take into account
all naturally existing physical situations for both the electron and the protons.
Such as the relativistic e¤ects due to the motion of the electron relative to
the nucleus (and vise versa) and the electrodynamic e¤ects. Consequently, we
11.3. PT APPLICATION II -THE REAL HYDROGENIC ATOM 287
have not dealt with the real Hydrogenic atom yet. In this section we will see
the application of PT theory by solving the eigenvalue equation for the real
hydrogenic atoms that leads to various corrections to the energy of the electron.
11.3.1 Relativistic Corrections

We recall that any classical system is described by the Hamiltonian
H0 = K + V; (11.156)
where K is the kinetic energy and V is the potential energy. In going to a

quantum description of this system what we have done is replacing K and
V by the corresponding operators either in position space (K ^ (~r) + V (~r)) or
momentum space (K ^ (~
p) + V (~
p)). For most of the physical systems that we
have studied, we used the position space representation of these operators. For
Hydrogenic atoms, what we considered is only the kinetic energy of the electron
which we represent in the position space by
2
^ 0 = pê :
K (11.157)
2me
and the electrostatic potential energy
1 Ze2
V^ (~r) = (11.158)
4 0 r
and we used the quantum Hamiltonian
2
^ 0 = pê 1 Ze2
H ; (11.159)
2me 4 0 r
This form of the Hamiltonian neglects the kinetic energy due to the motion of
the relative motion of the protons and does not integrate the relativistic e¤ects.
Taking the motion of the proton into account one should then write the
Kinetic energy operator as
K = Ke + Kp : (11.160)
In order to include relativistic e¤ects we use the relativistic kinetic energy
K=E E0 (11.161)
where E0 is the rest mass energy
E0 = m0 c2 (11.162)
and E is the relativistic total energy which can be expressed in terms of the
relativistic momentum, p;as
q
2
E = p2 c2 + (m0 c2 ) : (11.163)
Using this expression for the relativistic energy one can express the relativistic
kinetic energy as
2s 3
q 2
2 p
K = p2 c2 + (m0 c2 ) m0 c2 = m0 c2 4 1 + 15 : (11.164)
m0 c
Applying the series expansion

1
X p p(p 1) 2
(1 + x)p = xn = 1 + px + x :::; (11.165)
n 2!
n=1
we have
1 1 2
(1 + x)1=2 = 1 + x x ::: (11.166)
2 8
so that for x << 1 (i.e. mp0 c << 1), one can make the approximation
" # 2
2 4
2 1 p 1 p p2 p2
K ' m0 c = ; (11.167)
2 m0 c 8 m0 c 2m0 8m30 c2
We making the transition from classical to quantum by replacing the momentum

p with its operator p^: Thus the kinetic energy operator for the electron becomes
2
2
^ e = pê p^2e
K ; (11.168)
2me 8m3e c2
and for the proton
2
p^2p p^2p p^2p
^p =
K ' ; (11.169)
2mp 8m3p c2 2mp
where for the proton, due to it heavy mass, pp << mp c; we have neglected the
relativistic correction. Thus with relativistic correction the total kinetic energy
operator can be expressed as
2
2 p^2 p^2e
^ =K
K ^ p = pê + p
ê + K : (11.170)
2me 2mp 8m3e c2
The expression can be put in the form
mp
^2e + mem+m
me +mp p
e
p^2
p p
p^2e
2
p^2 p^2e
2
^ =
K m m = ; (11.171)
2 mee+mpp 8me c3 2 2 8m3e c2
where
me mp
= (11.172)
me + mp
is known as the reduced mass and
mp me
p^2 = p^2 + p^2 : (11.173)
me + mp e me + mp p
Note that p^ can be interpreted as the momentum operator describing the cen-
ter of mass motion. Then quantum Hamiltonian for a Hydrogenic atom with
relativistic correction becomes
2
^ + V^ = p^
^ =K
2
1 Ze2 p^2e
H : (11.174)
2 4 0 r 8m3e c2
or
^ =H
H ^0 + H
^ 1: (11.175)
^ 0 is the unperturbed Hamiltonian for the Hydrogenic atom,
where H
2
^ 0 = p^ 1 Ze2
H ; (11.176)
2 4 0 r
^ 1 the Hamiltonian resulted from the relativistic correction
and H
2
^1 = p^2e
H : (11.177)
8m3e c2
It is important to note that the unperturbed part of the Hamiltonian, H ^ 0 ; in

Eq. (11.176) is not exactly the same us the Hamiltonian (without the relativistic
correction) in Eq. (11.159). But the results we obtained for the Hamiltonian
in Eq. (11.159) (the eigen values and eigen functions) can be used by replacing
me with the reduced mass, (if it is necessary). Eq. (11.176) reduces to Eq.
(11.159)
me mp me
= = me ' me ;
me + mp 1+ mp
me
mp me 1 mp
p^2 = p^2e + p^2p = ^2e +
me p ^2p ' p^2e :
me p
me + mp me + mp 1+ m p
1 + mp
when we make the approximation,

me 1
= ' 0:
mp 1836:15267389
As we have done in the previous section we shall exploit commutation or

parity relations to determine the correction. To this end, one can easily show
that " #
h i p
^2 2 h i
H^ 1; L
^ = e
; ^ = p^2 2 ; L
L ^ =0 (11.178)
e
8m3e c2
so that
h i h i
h nl0 m0 j H^ 1; L
^ j nlm i =h nl0 m0 j
^H
L ^1 ^ 1L
H ^ j nlm i
= (L (l0 ; m0 ) L (l; m)) h nl0 m0 j H1

^ j nlm i = 0: (11.179)
There follows that for l0 6= l , m0 6= m, or both l0 6= l and m0 6= m; we must have
h nl0 m0 j H1
^ j nlm i =0 (11.180)
The result in Eq. (11.183) shows that although the eigenstates for the unper-
turbed system are highly degenerate the matrix representation of the perturbing
Hamiltonian in each degenerate subspace that we obtain from
X D E
(j) ^
i n H1 (i)
n = j En(1) : (11.181)
i
is already diagonal and we can calculate the …rst order energy shift by simply
…nding
(1) ^ 1 j nlm i :
E1 = h nlm j H (11.182)
^ 1 ; in Eq. (11.177) as
Using Eq. (11.159) one can rewrite, H
2 2 2
^1 = p^2e 1 p^2e 1 ^ 0 + 1 Ze
2
H = = H ; (11.183)
8m3e c2 2me c2 2me 2me c2 4 0 r
so that one …nds
2
(1) ^ 1 ^ 1 Ze2
E1 =h nlm j H1 j nlm i = h nlm j H0 + j nlm i
2me c2 4 0 r
" 2
1 ^2 1 Ze2
= h nlm j H0 j nlm i +h nlm j j nlm i
2me c2 4 0 r
Ze2 ^ 1 + 1H^0 j
+ h nlm j H0 nlm i (11.184)
4 0 r r
Homework: Show that
h nlm j
^0 1 + 1 H
H ^0 j nlm i = 2En0 h nlm j
1
j nlm i
r r r
Using the result in the HW problem, one …nds
" 2
#
(1) 1 0 2 Ze2 1 0 Ze
2
1
E1 = En + h nlm j 2 j nlm i + 2En h nlm j j i
2me c2 4 0 r 4 0 r nlm
(11.185)
Noting that
Z1 Z 2 Z
1 k+2 2 2
h nlm j k j nlm i = drr jRnl (r)j d' sin ( ) jYlm ( ; ')j d
r 0 0
0
Z1
2
= drrk+2 jRnl (r)j (11.186)
0
Substituting
l
2Zr Zr 2Zr
Rnl (r) = e a0 n
Hn ; (11.187)
a0 n a0 n
we may write
Z1 2l
1 2Zr 2Zr 2Zr
h nlm j j nlm i = drrk+2 e a0 n
Hn2 (11.188)
rk a0 n a0 n
0
which gives
a0
h nlm j r j nlm i 3n2 l (l + 1) ;
=
2Z
a2 n2
h nlm j r2 j nlm i = 0 2 5n2 + 1 3l (l + 1) ;
2Z
1 Z 1 Z2
h nlm j j nlm i = 2
; h nlm j 2 j nlm i = 2 3 1 ;
r a0 n r a0 n l + 2
1 Z3
h nlm j j nlm i = : (11.189)
r3 a30 n3 l l + 21 (l + 1)
Then the energy shift in Eq. (11.185) becomes

" 2
(1) 1 2 Ze2 Z2
En = En0 + 1
2me c2 4 0 a20 n3 l+ 2
Ze2 Z
+2En0 (11.190)
4 0 a0 n2
Using the energy for a Hydrogenic atom we determined in Chapter 9,
2
me c2 (Z )
En0 = (11.191)
2 n2
we may write
2 !2 !
2 2
1 4 me c2 (Z ) me c2 (Z ) Ze2 Z
En(1) = 2
2me c2 2 n2 2 n2 4 0 a0 n2
2
#
Ze2 Z2
+ 1 (11.192)
4 0 a20 n3 l+ 2

" #
2 2
1 2 2 (Z ) 3 (Z )
En(1) = 2
me c (Z ) (11.193)
2 n3 (2l + 1) 4n4
Equation (11.193) is the energy correction for an electron in a hydrogenic atom

Figure 11.5: Energy spectrum for the …rst excited state (n=2) in a Hydrogenic
atom with relativistic correction.
due to relativistic correction to the kinetic energy of both the electron and
proton. For the ground state (n = 1 ) l = 0), we …nd
" #
2
(1) 1 2 2 2 3 (Z ) 5 4
E1 = me c (Z ) 2 (Z ) = me c2 (Z ) (11.194)
2 4 8
nothing happens to the energy level as one should expect. However, for the …rst
excited state (n = 2 ) l = 0; 1), we …nd
1 1 3 1 13
(1)
E2 = me c2 (Z )
4
= me c2 (Z )
4 16 ;
l=0
7
8 (2l + 1) 16 8 48 ;
l=1
(11.195)
This clearly shows that (see Fig. 11.5) the removal of the degeneracy due to
l (= 0; 1) for the …rst excited state when we made the relativistic correction.
Here also, through the correction we found are two di¤erent values, we see three
energy levels for similar reason we discussed in the previous section.
11.3.2 Spin-orbit coupling correction

In relativistic electrodynamics (refer to Theo. Phys. III Sec 11.2-5 ) magnetism
is a relativistic phenomenon. What is measured as electrical in one reference
frame could turn out to be magnetic in another reference frame. Due to the
electric …eld of the proton, according to relativistic electrodynamics theory, an
electron moving with uniform velocity, ~v ; experiences a magnetic …eld given by
~v ~
E
~ =
B (11.196)
c2
where is the electric …eld of the proton at the position of the moving electron.
Due to this magnetic …eld interaction with the spin of the electron and its
associated magnetic moment there is a change in energy of the electron. Using

the expression for the electric …eld in terms of the electric potential of the proton
at the position of the electron
Ze 1
V (~r) = (11.197)
4 0r
for the electric …eld we have
~ = Ze 1 Ze ~r
E rV (~r) = r = (11.198)
4 0r 4 0 r3
so that the magnetic …eld can be written as
~ = 1 Ze ~r Ze
B 2
~v = (me~v ~r)
c 4 0 r2 4 2 3
0 me c r
Ze
= (~r me~v ) : (11.199)
4 0 me c2 r3
Using the orbital angular momentum
~ = ~r
L me~v = ~r p~e (11.200)
we can express the magnetic …eld as
~ = Ze ~
B 2 3
L: (11.201)
4 0 me c r
The magnetic moment of the electron which is given by

e ~ e ~
m
~ = gS = S
2me me
interacts with the magnetic …eld in Eq. (11.201). This interaction energy is
given by
Ze2 ~ L
S ~
H1 = m ~ B ~ = : (11.202)
4 0 m2e c2 r3
In terms of the total angular momentum
J~ = L
~ + S;
~ J z = Lz + S z (11.203)
we may write
~ S
J 2 = L2 + S 2 + 2 L ~ )L ~ = 1 J2
~ S L2 S2 (11.204)
2
The quantum Hamiltonian due to the spin-orbit coupling can then be expressed
as
^1 = Ze2 S^ L ^
H 2 2 3
; (11.205)
4 0 me c r
where
S^ L b = 1 J^2 L ^ 2 S^2 : (11.206)
2
We use the degenerate perturbation theory to determine the energy shift due to
this spin-orbit coupling. To this end, we recall in the degenerate perturbation
theory …rst-order correction in energy is given by
X D E
(j) ^ (i)
i n H 1 n = j En(1) : (11.207)
i
In solving this equation we need to be aware that the perturbing Hamiltonian

involves the intrinsic spin operator. The eigenvalue equation we did solve for the
unperturbed Hydrogenic atom did not include the intrinsic spin of the electron
and the energy eigen state that we found for the unperturbed system,
j nlm i = jn; l; mi (11.208)

E
does not include the intrinsic spin state. In solving Eq. (11.207), (i) n must
include the eigen state associated with the intrinsic spin of the electron. Thus
we must write this energy eigen state as tensor product of the energy eigen
states for the unperturbed Hydrogenic atom and the intrinsic spin states. An
electron is a spin half particle and from Chapter 4, we recall that from the
eigenvalue equation
S^2 jjs ; ms i = ~2 js (js + 1) jjs ; ms i ; S^z jjs ; ms i = ~ms jjs ; ms i
we found the intrinsic spin state for an electron are

1 1 1 1
j 1i = ; ;j 2i = ;
2 2 2 2
where
1 1 1
) ms =
js = ; :
2 2 2
Then one can write the energy eigen state for the unperturbed Hamiltonian as
E jn; l; mi 1 1
(i)
= jn; l; mi j i = jn; l; m; i = 2; 2 (11.209)
n k k 1 1
jn; l; mi 2; 2
and the …rst order correction to the energy can be express as

n
X1 l
X 2
X
lmk hn; l0 ; m0 ; ^ jn; l; m;
k0 j H1 ki = (1)
l 0 m0 k 0 En : (11.210)
l=0 m= l k=1
Let’s check for the operators associated with the degeneracy commutes with the
perturbing Hamiltonian. One operator associated with the degeneracy is L ^2
and it does commute with perturbing Hamiltonian
h i h i
^ 1; L
H ^ 2 = S^ L;
^ L^ 2 = 0: (11.211)
Thus
h i h i
n; l0 ; m0 ; H^ 1; L
^ 2 jn; l; m; k0 i = hn; l0 ; m0 ; k0 j
^ 1L
H ^2 ^2H
L ^ 1 jn; l; m; ki
h i
= 0 ) hn; l0 ; m0 ; k0 j
^2H
L ^1 ^ 1L
H ^ 2 jn; l; m; ki =0
~2 [l0 (l0 + 1) l (l + 1)] hn; l0 ; m0 ; ^ jn; l; m;
k0 j H1 ki = 0: (11.212)
There follows that

hn; l0 ; m0 ; ^ jn; l; m;
k 0 j H1 ki =0 (11.213)
for all l0 6= l: Furthermore, for the z-component of the total angular momentum
operator
J^z = L
^ z + S^z (11.214)
one can show that
h i h i h i
H^ 1 ; J^z = S^ L;
^ J^z = S^ L;
^ L^ z + S^z = 0: (11.215)
Taking into account the result we obtained in Eq. (11.213),where we have shown
l0 = l to have a none zero value for the matrix element for H ^ 1 one can write
h i
hn; l; m0 ; k0 j H ^ 1; L
^ z + S^z jn; l; m; k i = 0
h i
) hn; l; m0 ; k0 j H ^1 L ^ z + S^z L^ z + S^z H^ 1 jn; l; m; k i = 0
h i
) hn; l; m0 ; k0 j L ^ z + S^z H ^1 H ^1 L ^ z + S^z jn; l; m; k0 i = 0 = 0
(11.216)
Noting that
^ z jn; l; m; ^ z jn; l; mi 1 1 1 1
L ki = L ; = m~ jn; l; mi ;
2 2 2 2
^ z jn; l; m;
) L ki = m~ jn; l; m; k i ;
1 1 ~ 1 1
S^z jn; l; m; ki = jn; l; mi S^z ; = jn; l; mi ;
2 2 2 2 2
) S^z jn; l; m; ki = msk jn; l; m; ki ; (11.217)
where
1 1
ms1 = ; ms2 = :
2 2
one can then rewrite Eq. (11.216) as
~ [(m0 + msk0 ) (m + msk )] hn; l; m0 ; k0 j H1

^ n; l; m; = 0:
k
There follows for

m0 + msk0 6= m + msk
we must have E
hn; l; m0 ; ^
k0 j H1 n; l; m; = 0:
k
Therefore, the possible none zero element of the matrix are when
m0 + msk0 = m + msk ) m0 = m + msk msk0 :
Using
1 1
ms1 = + ms2 = ;
2 2
one …nds
8 1 1
>
> m+ 2 2 =m
< 1 1
0 m+ 2 + 2 =m+1
m = m + msk msk0 = 1 1 (11.218)
> m
> 2 2 =m 1
: 1 1
m 2 + 2 =m
1 1
m+ =m
) m0 = 2
1
2
1 ; (11.219)
m+ 2 + 2 =m+1
Note that we used the fact that
m0 = m 1 ) m = m0 + 1: (11.220)
^ 1 exist only for the two states

Therefore the none zero matrix elements for H
1 1
jn; l; m; 1i = jn; l; mi ; ; (11.221)
2 2
1 1
jn; l; m + 1; 2i = jn; l; m + 1i ; (11.222)
2 2
and …rst order correction determined by

X D E
(j) ^ (i) (1)
i n H1 n = j En
i
n
X1 l
X 2
X
) lmk hn; l0 ; m0 ; k0 j H1
^ jn; l; m; ki = (1)
l0 m0 k0 En : (11.223)
l=0 m= l k=1
reduces to
1 hn; l; m; ^ jn; l; m;
1 j H1 1i + 2 hn; l; m; ^ jn; l; m + 1;
1 j H1 2i
(1)
= 1 En ;
1 hn; l; m + 1; ^ jn; l; m;
2 j H1 1i + 2 hn; l; m + 1; 2 j H1
^ jn; l; m + 1; 2i
(1)
= 2 En ; (11.224)
which can be rewritten, using matrices, as
^ 1 jn; l; m; 1 i
hn; l; m; 1 j H ^ 1 jn; l; m + 1; 2 i
hn; l; m; 1 j H
hn; l; m + 1; 2 j H^ 1 jn; l; m; 1 i hn; l; m + 1; 2 j H^ 1 jn; l; m + 1; 2 i
1 (1) 1
= E2 : (11.225)
2 2
Next we proceed to determine these matrix element by applying the raising

and lowering operators we were introduced in chapter four. For the orbital
angular momentum operators we can write the lowering and raising operators
as
^ =L
L ^ x iL^y (11.226)
which leads to the relations

h i h i h i
L^+; L
^ = 2~L ^z; L^z; L
^ = ^ ; L
~L ^2; L
^ =0
^+L
L ^ =L
^ 2x + L
^ 2y + ~L
^z; L
^ L
^+ = L
^ 2x + L
^ 2y ^z:
~L (11.227)
We can also establish a similar expressions for the spin angular momentum
operators. Applying these relations one can show that
2 S^ L
^ =L
^ + S^ + L
^ S^+ + 2L
^ z S^z : (11.228)
Homework # 2: Show that
2 S^ L
^ =L
^ + S^ + L
^ S^+ + 2L
^ z S^z : (11.229)
so that the perturbing Hamiltonian
Ze2 2 S^ L^
Ze2 1 ^ ^
^1 =
H = L+ S + L^ S^+ + 2L ^ z S^z ;
8 0 m2e c2 r3 8 0 m2e c2 r3
(11.230)
We also recall the action of the lowering and raising operators to the angular
momentum eigen states
p
L^ jl; mi = ~ (l(l + 1) m (m 1)) jl; m 1i ; (11.231)
^
Lz jl; mi = ~m jl; mi ; (11.232)
so that
^ + S^ + L
L ^ S^+ + 2L
^ z S^z jn; l; m + 1; 2i
^ + S^ jn; l; m + 1;
=L 2i
^ S^+ jn; l; m + 1;
+L 2i
^ z S^z jn; l; m + 1; 2 i :
+ 2L
(11.233)
Using
1 1
jn; l; m + 1; 1i = jn; l; m + 1i ;
2 2
1 1
jn; l; m + 1; 2i = jn; l; m + 1i ; (11.234)
2 2
we can easily …nd
S^ jn; l; m + 1; 2i =0 (11.235)
and
1 1
S^+ jn; l; m + 1; 2 i = jn; l; m + 1i S^+ ;
2 2
s
1 1 1 1 1 1
=~ ( + 1) + +1 jn; l; m + 1i ;
2 2 2 2 2 2
) S^+ jn; l; m + 1; 2i = ~ jn; l; m + 1; 1i (11.236)
and
1 1
S^z jn; l; m + 1; 2i = jn; l; m + 1i S^z ;
2 2
~ 1 1
= jn; l; m + 1i ;
2 2 2
~
) S^z jn; l; m + 1; 2i = jn; l; m + 1; 2i : (11.237)
2
Using the results above, for
^ + S^ + L
L ^ S^+ + 2L
^ z S^z jn; l; m + 1; 2i
^ + S^ jn; l; m + 1;
=L 2i
^ S^+ jn; l; m + 1;
+L 2i
^ z S^z jn; l; m + 1;
+ 2L 2i : (11.238)
we …nd
^ + S^ + L
L ^ S^+ + 2L
^ z S^z jn; l; m + 1; 2i
^ jn; l; m + 1;
= ~ L 1i
^ z jn; l; m + 1;
L 2i : (11.239)
Following a similar procedure for the lowering and z-component operator for the
orbital angular momentum one …nds
p
^ jn; l; m + 1; 1 i = ~ (l(l + 1) (m + 1) m) jn; l; m; 1 i
L
^ z jn; l; m + 1; 2 i = ~ (m + 1) jn; l; m + 1; 2 i :
L (11.240)
which leads to
^ + S^ + L
L ^ S^+ + 2L
^ z S^z jn; l; m + 1; 2 i
p
= ~2 (l(l + 1) (m + 1) m) jn; l; m; 1 i (m + 1) jn; l; m + 1; (11.241)
2i :
and
^ 1 jn; l; m + 1; 2 i
hn; l; m; 1 j H
Ze2 1 ^ ^ ^ ^ ^ ^
= hn; l; m; 1 j 3 L + S + L S+ + 2Lz Sz jn; l; m + 1; 2i
8 0 m2e c2 r
Ze2 ~2 p 1
= 2 2
(l(l + 1) (m + 1) m) hn; l; m; 1 j 3 jn; l; m; 1 i
8 0 me c r
1
(m + 1) hn; l; m; 1 j 3 jn; l; m + 1; 2 i
r
Taking the orthonormality of the intrinsic spin and the z-component of the
orbital angular momentum eigen states one can show that
1
hn; l; m; 1j jn; l; m + 1; 2i =0
r3
and
1 1
hn; l; m; 1j 3
jn; l; m; 1 i = hn; l; mj 3 jn; l; mi
r r
Z1 Z 2 Z Z1
2 2 2
= drr jRnl (r)j d' sin ( ) jYlm ( ; ')j d = drr jRnl (r)j
0 0
0 0
1 Z3
) hn; l; m; 1 j 3 jn; l; m; 1 i = (11.242)
r a30 n3 l l + 12 (l + 1)
so that using the result in Eq. (11.189), we …nd

p
^ 1 jn; l; m + 1; 2 i = F (r) ~2 (l(l + 1)
hn; l; m; 1 j H (m + 1) m)
where
Ze2 Z3
F (r) =
8 0 me c a0 n l l + 21 (l + 1)
2 2 3 3
Using the Hermiticity of the perturbing one can also …nd Hamiltonian we have
hn; l; m + 1; 2 j H1
^ jn; l; m; 1i = hn; l; m; 1 j H1
^ jn; l; m + 1; 2i
Homework # 3: Following a similar procedure show that
hn; l; m; ^ jn; l; m;
1 j H1 1i = ~2 mF (r) ; (11.243)
hn; l; m + 1; ^ jn; l; m + 1;
2 j H1 2i = 2
~ (m + 1) F (r)
Then the eigen value equation

^ 2 jn; l; m; 1 i
hn; l; m; 1 j H ^ 2 jn; l; m + 1; 2 i
hn; l; m; 1 j H
hn; l; m + 1; 2 j H^ 2 jn; l; m; 1 i hn; l; m + 1; 2 j H^ 2 jn; l; m + 1; 2 i
1 (1) 1
= E2 : (11.244)
2 2
becomes
p
2 p m l (l + 1) m (m + 1)
F (r) ~
l (l + 1) m (m + 1) (m + 1)
1 (1) 1
= E2 : (11.245)
2 2

p
p m l (l + 1) m (m + 1)
l (l + 1) m (m + 1) (m + 1)
1 1
= : (11.246)
2 2
and the energy correction is given by

(1)
E2 = F (r) ~2 :
There follows that

p
p m l (l + 1) m (m + 1)
det =0 (11.247)
l (l + 1) m (m + 1) (m + 1)
2
) + l (l + 1) = 0 (11.248)
which leads to the following eigenvalues and eigenvectors

r r
l+m+1 l m
1 = l; j 1 i = jn; l; m; 1 i + jn; l; m + 1; 2 i
2l + 1 2l + 1
r r
l m l+m+1
2 = (l + 1); j 2 i = jn; l; m; 1 i jn; l; m + 1; 2 i
2l + 1 2l + 1
(11.249)
Homework # 3: Determine the eigenvalues and eigenvectors for the matrix

p
p m l (l + 1) m (m + 1)
A= (11.250)
l (l + 1) m (m + 1) (m + 1)
Here we note that the eigenvectors j 1 i and j 2 i are also the eigen vectors for
^ 2 as well as S^2 as these vectors are a linear superposition of the eigenvectors
L
^ 2 as well as S^2 :
jn; l; m; 1 i and jn; l; m + 1; 2 i which are the eigenvectors of L
Therefore, we can say that the eigenvectors j 1 i and j 2 i are also the eigenvec-
tors for the total angular momentum operators which is linear combination of
the operators L ^ 2 ; S^2 ; and 2 S^ L
^ given by
J^2 = L
^ 2 + S^2 + 2 S^ L
^ : (11.251)
Thus from
J^2 j i = L
^ 2 + S^2 2 S^ L
^ ^ 2 j i + S^2 j i + 2 S^ L
j i=L ^ j i : (11.252)
we may write
1 1 l
j(j + 1) = l(l + 1) + ( + 1) + : (11.253)
2 2 (l + 1)
which leads to the total angular momentum values
1
l+ 2
j= 1 : (11.254)
l 2
This shows that the S^ L

^ interaction term has coupled the orbital angular
momentum, l; with the spin angular momentum, 21 to produce the total angular
momentum j that takes on the values l + 21 and l 12 : In terms of j in Eq.
(11.254) and
1
mj = m + (11.255)
2
we may write the eigenvectors
r r
l+m+1 l m
j 1i = jn; l; m; 1 i + jn; l; m + 1; 2 i
2l + 1 2l + 1
r r
l m l+m+1
j 2i = jn; l; m; 1 i jn; l; m + 1; 2 i (11.256)
2l + 1 2l + 1
as
1
j 1i = j = l + ; mj
2
s s
1 1
l + mj + 2 1 l mj + 2 1
= n; l; mj ; + n; l; mj + ; ;
2l + 1 2 1 2l + 1 2 2
(11.257)
1
j 2i = j=l ; mj
2
s s
1 1
l mj + 2 1 l + mj + 2 1
= n; l; mj ; 1 n; l; mj + ; 2 :
2l + 1 2 2l + 1 2
(11.258)
The energy correction due to spin-orbit coupling would then be
En(1) = F (r) ~2
!
Z 4 e 2 ~2 1 l; for j = l + 12
= ; (11.259)
8 2 2 3 3
0 me c a0 n l l + 12 (l + 1) (l + 1) ; for j = l 21
where we substituted
Z 4 e2 1
F (r) =
8 0 me c a0 n l l + 21 (l + 1)
2 2 3 3
And using
e2
= ; (11.260)
4 0 ~c
we may write
!
~3 cZ 4 1 l; for j = l + 12
En(1) = ;
2m2e c2 a30 n3 l l+ 1
2 (l + 1) (l + 1) ; for j = l 12
(11.261)
Furthermore, if use the Bohr radius
~
a0 = (11.262)
me c
the energy correction can be expressed as
!
1 4 1 l; for j = l + 12
En(1) = me c2 (Z ) ;
2 3
n l (l + 1) l + 1
2
(l + 1) ; for j = l 12
(11.263)
Next we proceed to analyze both the relativistic and spin-orbit coupling cor-
rections for the …rst excited state, n = 2. First let’s examine the spin-orbit
coupling correction, Eq. (11.259) for
l = 0 ) j = 21 ; 12
n=2) (11.264)
l = 1 ) j = 12 ; 32
which becomes 8 1
(Z )
4 < 0 j= 2
(1)
E2 = me c2 1
j= 3
; (11.265)
16 : 32 2
1
3 j= 2
Note that though Eq. (11.259) shows none zero value for l = 0, we have set
(1)
E2 = 0 since there is no spin-coupling for l = 0:This has been shown using
more exact relativistic wave functions from the Dirac equation which is beyond
the scope of this class. It was shown by We now consider the total shift due
to both spin-coupling and relativistic correction. We recall that the relativistic
correction is given by
" #
2 2
(1) 1 2 2 2 (Z ) 3 (Z )
En = me c (Z ) (11.266)
2 n3 (2l + 1) 4n4
Then the total energy shift would be
" #
4
(1) 1 2 (Z ) l
En = me c
2 n3 l (l + 1) l + 21 (l + 1)
" #
4 4
1 2 (Z ) 3 (Z )
me c2 ; (11.267)
2 n3 (2l + 1) 4n4
Figure 11.6: Energy spectrum for the …rst excited state with spin-orbit correc-
tion only.

( )
4 4
1 2 (Z ) l 3 (Z )
En(1) = me c2 1 + ; (11.268)
4 n3 l (l + 1) l + 2
(l + 1) 2n4
The energy spectrum for the …rst excited state for a hydrogenic atom with spin-
orbit coupling correction is shown in Fig. 11.6When we add both the relativistic
and spin–orbit corrections the energy spectrum for the ground state is shown
in Fig. 11.7 NB: There is one additional correction known as the Darwin term
Figure 11.7: Energy spectrum for the …rst excited state in a hydrogenic atom
with relativistic, spin–orbit coupling, and Darwins corrections.
(added in Fig. 11.7). It is derived from the non-relativistic expansion of the

Dirac equation. The Darwin term a¤ ects only the s orbitals. We will get intro-
duced to the Dirac equation when we get into relativistic quantum mechanics.
11.4 PT Application III -The Zeeman e¤ ect

As a last application of perturbation theory we study two e¤ects in the energy
spectrum of the electron in a hydrogenic atom due to an external magnetic
…eld and the spin of the nucleus. The e¤ect resulting from an applied external
magnetic …eld is known as the anomalous zeeman e¤ ect and the e¤ect caused
by the magnetic …eld created due to the spin of the nucleus is referred as the
hiper…ne structure.
11.4. PT APPLICATION III -THE ZEEMAN EFFECT 305
11.4.1 The anomalous zeeman e¤ect

In a hydrogenic atom there is one electron. This electron posses both the orbital,
~ L ; and spin magnetic moments, ~ S ; due to its orbital and Intrinsic spin angular
momenta. The orbital magnetic moment can be expressed in terms of the orbital
angular momentum as
e ~
~L = L: (11.269)
2me
We recall from chapter one that Magnetic moment due to Intrinsic spin is given
by
gq ~
~S = S; (11.270)
2me
where the value of the constant g is
8
< 2:00; electron
g= 5:58; proton (11.271)
:
3:82; neutron
Then spin magnetic moment of the electron becomes

e ~
~S = S; (11.272)
me
so that the total magnetic moment, ~ J ; becomes

e ~ + 2S
~ = e
~J = L J~ + S
~ ; (11.273)
2me 2me
where we used is the total angular momentum
J~ = L
~ +S
~)L
~ = J~ ~
S: (11.274)
When a hydrogenic atom is placed in an external uniform magnetic …eld, B; ~ the

electron interacts with the …eld due to its total magnetic moment. The resulting
interaction energy is determined by
~ = e
HB = ~J B J~ + S
~ ~
B; (11.275)
2me
For the real hydrogenic atom (with spin-orbit coupling corrections), the total
quantum Hamiltonian would then become
2
1 Ze2 Ze2 ~ L~
^ = p^
H +
S
+
e
J~ + S
~ ~
B: (11.276)
2me 4 0 r 2 2
4 0 me c r 3 2me
In the previous section we have determined the eigen functions and the eigen-
values for a Hydrogenic atom with the spin-orbit coupling is taken into account,
^ 0 jn; j; mj ; li = E jn; j; mj ; li ;
H (11.277)
where
2
1 Ze2 Ze2 ~ L~
^ 0 = p^
H +
S
(11.278)
2me 4 0 r 2 2
4 0 me c r 3
Then the quantum Hamiltonian for a hydrogenic atom in a magnetic …eld can
be expressed as
H^ =H ^0 + H^ 1; (11.279)
where the perturbing Hamiltonian is
^1 = e
H J~ + S
~ ~
B: (11.280)
2me
~ = B z^, (see Fig.11.8)the
For a magnetic …eld directed parallel to the z-axis, , B
Figure 11.8: A real hydrogen atom in uniform magnetic …eld.
perturbing part of the Hamiltonian can be rewritten as
^ 1 = eB J^z + S^z :
H (11.281)
2me
We can then determine the …rst order energy shift due to this perturbing Hamil-
tonian using the energy eigen functions of the unperturbed hydrogenic atom with
the spin-orbit coupling corrections by evaluating
EB ^ 1 jj; mj ; li = eB hj; mj ; lj J^z + S^z jj; mj ; li

= hj; mj ; lj H
2me
eB h i
= ~mj + hj; mj ; lj S^z jj; mj ; li (11.282)
2me
where we used
J^z jj; mj ; li = ~mj jj; mj ; li : (11.283)
We determine the eigenvalue of S^z using an intuitive approach which has a
general applicability that can be established quite rigorously which we do not
do here. Though S^ and L ^ do not commute with the total Hamiltonian, H;^ the
total angular momentum operator,
J^ = L
~ + S;
~ (11.284)
^
does commute with H:
2
1 Ze2 Ze2 ~ L~
^ = p^
H +
S
+
e
J~ + S
~ ~
B: (11.285)
2me 4 0 r 2 2
4 0 me c r 3 2me
Homework Problem #1 h i
^H
J; ^ =0 (11.286)
Then applying the Haisenberg equation, one can write

d D Ê i Dh ^ ^ iE
J = J; H = 0: (11.287)
dt ~
which means the total angular momentum is conserved while S^ and L ^ are not
(since these operators do not commute with the total Hamiltonian). These
vectors each have a …xed length so that they precess about the direction of J^
(See Fig.11.9). These vectors (S^ and L)
^ each have a …xed length (magnitude), so
~ spin (S),
Figure 11.9: Orbital (L), ~ and total angular momentum (J~ = L
~ + S).
~
^ The components
that they precess (di¤erent direction) about the direction of J.
of S^ and L
^ along J^ ( i.e.S^jj and L
^ jj ) are …xed, while the other components,
rotating as they do about J^ axis, average to zero. One can see this, for example,
by considering the spin up (s = 21 ~) case closely as shown in Fig.11.10 where we
rotate the coordinate system such that the z-axis directed along the direction
of the total angular momentum.
Figure 11.10: A spin and orbital angular momentum precessing about the total
angular momentum.
S^ = S^? + S^jj ; L
^=L
^? + L
^ jj ; (11.288)
where
S^jj = S^ cos 00 ; L ^ jj = L
^ cos ( 0 ) (11.289)
S^? = S^ sin 00 cos (!t0 ) x ^ + S^ sin 00 sin (!t0 ) y^;
^? = L
L ^ sin ( 0 ) cos (!t) x
^+L ^ sin ( 0 ) sin (!t) y^;
where ! is the precession angular speed of S^ and L ^ about the direction of J.

^
From equation (11.289), we note that the time average values for the components
normal to J direction are zero for both S^ and L^
D E D E
S^jj = L ^ jj = 0; (11.290)
since
hcos (! 0 t)i = hsin (! 0 t)i = hcos (!t)i = hsin (!t)i = 0: (11.291)

Then one can easily see that

D E D E D E D E D E D E D E D E
S^ = S^? + S^jj = S^jj ; L
^ = L
^? + L
^ jj = L
^ jj (11.292)
which leads to the rule
S^ J^ S^ J^
S^ ! J^ = J^ (11.293)
J2 ~2 j (j + 1)
where we take into account that the total angular momentum is conserved and
is independent of time
d D Ê D E
J = 0 ) J^ = J = Constnat (11.294)
dt
From Eq. (11.293) follows that
S^ J^
S^z ! J^z (11.295)
~2 j (j + 1)
so that we may write
S^ J^ 1
S^z jj; mj ; li = J^z jj; mj ; li = J^z S^ J^ jj; mj ; li :
~2 j (j + 1) ~2 j (j + 1)
(11.296)
Noting that
^ = J^ 1 ^2 ^2
L S^ ) S^ J^ = J +S ^2 :
L (11.297)
2
so that
J^z ^2 ^2 ^ 2
J^z S^ J^ jj; mj ; li = J +S L jj; mj ; li
2
J^z 1 1
= ~2 j (j + 1) + +1 l (l + 1) jj; mj ; li
2 2 2
mj 3
) J^z S^ J^ jj; mj ; li = ~3 j (j + 1) + l (l + 1) jj; mj ; li (11.298)
2 4
Upon substituting the result in Eq. (11.298) into Eq. (11.296) we …nd
mj
~ j (j + 1) + 43 l (l + 1)
S^z jj; mj ; li = 2
jj; mj ; li : (11.299)
j (j + 1)
so that the energy shift in Eq. (11.282) becomes
eB h i
EB = ~mj + hj; mj ; lj S^z jj; mj ; li
2me
3
eB~mj j (j + 1) l (l + 1) + 4
= 1+ (11.300)
2me 2j (j + 1)
Homework: Find all the energy levels for the ground and the …rst excited
state for a hydrogen atom in a uniform magnetic …eld (apply Eq. (11.300))
with no relativistic correction included
Figure 11.11: The energy level for the …rst excited state in a Hydrogenic atom
in a uniform magnetic …eld with spin-orbit coupling, Darwin, and relativistic
corrections.
11.4.2 The hiper…ne structure

We have seen the e¤ect of an external …eld to a hydrogen-like atom. We now
look into the e¤ects due to magnetic interaction within the atom that lead to
very small energy shift (hyper…ne structure) compared to the spin-orbit coupling
shift (…ne structure). The magnetic interactions within the atom is the result
~N : The
of the spin of the nucleus (the proton). Let the spin of the nucleus be, S
the magnetic dipole moment for the nucleus, M ~ ; can then be expressed as
~ = ZegN S
M ~N ; (11.301)
2mN
where Z is the nuclear charge number, mN is the mass of the nucleus, and gN
is its gyromagnetic ratio. From Theo. Phys. III (Electricity & magnetism), the
magnetic …eld of a magnetic dipole with magnetic moment, M ~ ; is given by
~ N (~r) = 0 1 ~) ~ +8 ~ ;
B 3^
r(^
r M M (~r) M (11.302)
4 r3 3
(Problem 5.61 Gri¢ ths). Then at the position of the electron, ~r; the magnetic
…eld due to the spin of the nucleus can be expressed as
~N0 ZegN 0 1 ~N ) ~N + 8 ~N :
B = 3^
r(^
r S S (~r) S (11.303)
2mN 4 r3 3
Then the magnetic energy due to the interaction of the electron’s total magnetic
moment
e ~ + 2S~ ;
~J = L (11.304)
2me
with the nucleus magnetic …eld (the Hyper…ne perturbation) is given by
^N =
H ~
~J B N
Ze2 gN 0 1 ~N ) ~N + 8 ~N ~ + 2S
~ :
= 3^
r(^
r S S (~r) S L (11.305)
16 me mN r3 3
Using
1
c2 = ; (11.306)
0 0
one can then write the quantum Hamiltonian due to the magnetic interaction
of the Nucleus with the electron in a Hydrogenic atom can be expressed
2 3
2 r r^ S^N
3^ S^N
^ N = Ze
H
gN 4 +
8 ^
SN (~r)5 ^ + 2S^ : (11.307)
L
4 0 4me mN c2 r3 3
If we make the order of magnitude estimation
r r^ S^N
3^ S^N 8 ^ ~ ^
+ SN (~r) ; L + 2S^ ~;
r3 3 a30
where we used the Bohr radius, r ' a0 ; one may write

3
Ze2 ~cgN ~2 ~3 c Z cme
HN = Z
4 0 ~c 4me mN c2 a30 me mN ~
4 m e
= (Z ) me c2 ; (11.308)
mN
where
e2 ~
= ; a0 = : (11.309)
4 0 ~c me c
me
The result in Eq. (11.308) is a factor of mN smaller than the typical spin-orbit
coupling that we obtained
1 4
HSO (Z ) me c2 (11.310)
2
For a detailed calculation we are interested in the ground state where,n = 1; l =
^ + 2S^ = 2S)
0 (i.e.L ^ so that Eq. (11.307) reduces to
2
^ N = Ze
H
gN
4 0 2me mN c2
2 3
3 r^ S^ r^ S^N S^N S^ 8
4 + S^N S^ (~r)5 : (11.311)
r3 3
The energy shift can then be determined by evaluating
EN = hn; l; m; ^ jn; l; m;
k j HN ki (11.312)
which becomes
EN = h1; 0; 0; ^ j1; 0; 0;
k j HN ki (11.313)
To …nd the result in Eq. (11.312) we must …rst evaluate the integral
Z1
2
I = drr2 jR10 (r)j
0
2 3
Z 2 Z 3 r^ S^ r^ S^N S^N S^
4 8
d' + S^N S^ (~r)5
0 0 r3 3
2
sin ( ) jY00 ( ; ')j d : (11.314)
We noting that
1
r^ S^ r^ S^N = ~r S^ ~r S^N
r2
1
= (xSx + ySy + zSz ) (xSN x + ySN y + zSN z )
r2
1
= x2 Sx SN x + y 2 Sy SN y + z 2 Sz SN z + xy (Sx SN y + Sy SN x )
r2
+xz (Sx SN z + Sz SN x ) + zy (Sy SN z + Sz SN y )g ;
= sin2 ( ) cos2 (') Sx SN x + sin2 (') Sy SN y + cos2 ( ) Sz SN z
+ sin2 ( ) cos (') sin (') (Sx SN y + Sy SN x )
+ sin ( ) cos ( ) [cos (') (Sx SN z + Sz SN x ) + sin (') (Sy SN z + Sz SN y )] ;
(11.315)
where we used
x = r cos (') sin ( ) ; y = r sin (') sin ( ) ; z = r cos ( ) :
Furthermore, we have
2
2 1
jY00 ( ; ')j = p ; (11.316)
2
Thus one can write

Z 2 Z h i
2
d' 3 r^ S^ r^ S^N S^N S^ sin ( ) jY00 ( ; ')j d
0 0
Z 2 Z
1
= d' 3 r^ S^ r^ S^N sin ( ) d
4 0 0
Z 2 Z
2
S^N S^ d' sin ( ) jY00 ( ; ')j d
0 0
Z 2 Z
1
= 3 sin2 ( ) cos2 (') Sx SN x + sin2 (') Sy SN y
d'
4 0 0
Z
1
+r2 cos2 ( ) Sz SN z sin ( ) d S^N S^ r2 sin ( ) d ; (11.317)
2 0
where we have used
Z 2 Z 2 Z 2
cos (') sin (') d' = sin (') d' = cos (') d' = 0:
0 0 0
Furthermore using
Z 2 Z 2
cos2 (') d' = sin2 (') d' = :
0 0
we …nd
Z 2 Z h i
2
0 0
Z
1
= 3 (Sx SN x + Sy SN y ) sin2 ( ) + 2Sz SN z cos2 ( ) sin ( ) d
4 0
Z
1
S^N S^ sin ( ) d
2 0
Now integrating with respect to using
Z Z Z
2 4
cos2 ( ) sin ( ) d = ; sin2 ( ) sin ( ) d = ; sin ( ) d = 2:
0 3 0 3 0
The integral becomes
Z 2 Z h i
2
0 0
= Sx SN x + Sy SN y + Sz SN z S^N S^
Noting that
S^N S^ = Sx SN x + Sy SN y + Sz SN z
we …nd
Z 2 Z h i
2
d' 3 r^ S^ r^ S^N S^N S^ sin ( ) jY00 ( ; ')j d = 0
0 0
Therefore, we are left with the integral

Z1 Z 2 Z
2 2 8
I = drr2 jR10 (r)j jY00 ( ; ')j d' S^N S^ (~r) sin ( ) d
0 0 3
0
(11.318)
2 3
Z1 Z 2 Z
8 2 2
I=4 drr2 jR10 (r)j jY00 ( ; ')j (~r) d' sin ( ) d 5
3 0 0
0
S^N S^ (11.319)
Using the property of the Dirac delta function, we …nd

Z1 Z 2 Z
2 2 2 2
drr2 jR10 (r)j jY00 ( ; ')j (~r) d' sin ( ) d = jR10 (0)j jY00 (0; 0)j
0 0
0
Recalling that
3
Z 2
Zr 1
R10 (r) = 2 exp ; Y00 ( ; ') = p (11.320)
a0 a0 2
3 3
2 2 1 Z 1 Z cme
) jR10 (0)j jY00 (0; 0)j = = (11.321)
a0 ~
where we used
~
a0 =
me c
so that
3
8 Z cme
I= S^N S^ (11.322)
3 ~
The surviving part of the perturbing Hamiltonian after we calculated its expec-
tation value over the angular and orbital degrees of freedom would be
2 3
^ N = Ze gN Ze2 gN 8 Z cme
H 2
I= 2
S^N S^
4 0 2me mN c 4 0 2me mN c 3 ~
using
e2
= ; (11.323)
4 0 ~c
one …nds !
^N 4 4 me S^N S^
H = (Z ) me c2 gN :
3 mN ~2
Figure 11.12: The energy levels for an electron in a Hydrogenic atom for the
…rst excited state with spin-orbit and hyper…ne corrections.
Introducing the total spin operator (electron and the Nucleus)

F^ = S^ + S^N (11.324)
we may write
S^N S^ F^ 2 S2 2
SN
= (11.325)
~2 2~2
so that
S^N S^ F (F + 1) S (S + 1) SN (SN + 1)
j i= j i (11.326)
~2 2
where j i is the total spin eigen state which is also an eigen state of S and SN :
Thus the energy shift due to the magnetic …eld of the nucleus is given by
2 4 me
EN = (Z ) me c2 gN (F (F + 1) S (S + 1) SN (SN + 1)) (11.327)
3 mN
There follows that
(
1 4 me
3 (Z ) me c2 gN m ; for F = 1
EN = 4 2 me
N
(11.328)
(Z ) me c gN mN ; for F = 0
Figure 11.12 shows the energy spectrum for a hydrogenic atom for the …rst
excited state.
Homework: Find all the expressions for all the energies levels for the …rst
excited state shown in Fig. 11.12
Chapter 12
Many-particle systems
In this chapter we will study how the quantum mechanics of a single particle
is generalized to an N particle system. In particular we will focus on a two
particle system like the helium atom.
12.1 Many particle system Schrödinger equation

Consider a quantum mechanical system that consist of N particles with masses
m1 ; m2 ; m3 :::mN in one dimension (x-dimention). Suppose the position of the
particles at time, t; is described by x1 ; x2 ; x3 :::xN : The dynamics of this system
is governed by the Schrödinger equation
@ ^
i~ (x1 ; x2 ; x3 :::xN ; t) = H (x1 ; x2 ; x3 :::xN ; t) ; (12.1)
@t
^ is the quantum Hamiltonian given by
where H
XN XN
^ = p^2i 1 @2
H + V (^
x1 ; x
^2 ; x
^3 :::^
xN ) = ~2 + V (x1 ; x2 ; x3 :::xN )
i=1
2mi i=1
2mi @x2i
(12.2)
and (x1 ; x2 ; x3 :::xN ; t) is the wave function satisfying the normalization con-
dition Z Z Z
2
::: dx1 dx2 dx3 :::dxN j (x1 ; x2 ; x3 :::xN ; t)j = 1: (12.3)
The momentum and position operator do commute when these operators rep-
resent di¤erent particles. This means
[^
pi ; x
^j ] = i~ ij ; (12.4)
if pî refer to the momentum operator for the ith particle and x
^j is the position
operator for the j th particle.
317
318 CHAPTER 12. MANY-PARTICLE SYSTEMS
12.2 The two-particle system

For a system that consist of two particles we begin from the classical Hamiltonian
and also consider the three dimensional case such that one can write
p21 p2
H= + 2 + V (~r1 ; ~r2 ) : (12.5)
2m1 2m1
!
We introduce a momentum P and position !
r de…ned by
! !
P = p1+!
p 2; !
r =!
r1 !
r 2; (12.6)
and the position for the center of mass,

! m1 !
r 1 + m2 !
r2
R = ; (12.7)
M
where
M = m1 + m2
is the total mass for the two particles. Noting that
d!r d!
r1 d!
r2
= ) ~v = ~v1 ~v2 = ~v1 ~v2 ; (12.8)
dt dt dt
which we can express in terms of the momentum
!
p1 !
p2 m2 !
p 1 m1 !
p2
~v = = (12.9)
m1 m2 m1 m2
we may write the momentum, !
p ; conjugate to the relative position
!
r =!
r1 !
r 2;
as
! m1 m2 m2 !
p 1 m1 !p2 m2 !
p 1 m1 !
p2
p = ~v = ~v = = ; (12.10)
m1 + m2 m1 + m2 M
where
m1 m2
= : (12.11)
m1 + m2
is the reduced mass. Now using
! !
P = p1+!
p2 (12.12)
and
! m2 ! m1 !
p = p1 p 2; (12.13)
M M
we can easily show that
! m1 ! ! m2 !
p1 =!
p + P; p2 = !
p + P (12.14)
M M
12.2. THE TWO-PARTICLE SYSTEM 319
which leads to
p21 1 ! m1 ! ! m1 ! p2 m1 2 1 ! !
= p + P p + P = + P + p P (12.15)
2m1 2m1 M M 2m1 2M 2 M
and
p22 1 ! m2 ! ! m2 ! p2 m2 2 1 ! !
= p P p P = + P p P (12.16)
2m2 2m1 M M 2m2 2M 2 M
Thus the kinetic energy term in the Hamiltonian becomes
p21 p2 (m1 + m2 ) p2 P2 p2 P2
+ 2 = + = + ; (12.17)
2m1 2m1 2m1 m2 2M 2 2M
where we used the reduced mass in Eq. (12.11). Then the total quantum
Hamiltonian for a two particle system can be expressed as
2 ^2
^ = p^ + P + V ~r; R
H ~ : (12.18)
2 2M
where
m1 m2
= ; M = m1 + m2 ;
m1 + m2
! m2 ! m1 !
P = !
p1+! p 2; !
p = p1 p 2;
M M
! !
! m1 r 1 + m2 r 2
!
r = !
r1 ! r 2; R = : (12.19)
M
The eigenvalue equation for this Hamiltonian can then be written as
" #
p^2 P^ 2 ~ ~ =E ~ :
+ + V ~r; R ~r; R ~r; R (12.20)
2 2M
For a potential that depends only on the separation distance between the two
particles, we have
~ = V (~r)
V ~r; R
so that using separation of variables the solution to Eq. (12.20) can be expressed
as ~ ~
~ = e iP~ R u (~r)
~r; R (12.21)
where P~ is the eigenvalue of P^ and u (r) satis…es the equation

p^2 P2
+ V (~r) u (r) = E u (r) (12.22)
2 2M
that we obtain after we do the separation of variables. The result in Eq. (12.22)
is a one particle equation for a particle with reduced mass ; moving in the
potential V (~r) ;and energy E reduced by the kinetic energy of the two-particle
system (center of mass of kinetic energy??? )
Homework Problem 1: show that Eq. (12.21) is the solution to Eq. (12.20)
12.3 Identical particles and the exchange oper-

ator
Electrons are indistinguishable (identical) particles. Indistinguishability is a
purely quantum mechanical property. In classical mechanics it is, in principle,
possible to follow the trajectories of all particles so that they are never really
be indistinguishable. But in a quantum system any attempt to keep track of
the particle by measuring its position, for example, is bound to change funda-
mentally the particles quantum state. In order to see what types of states are
allowed for a quantum system made of two or more identical particles like the
electrons, we …rst learn about an important operator in quantum mechanics
known as the exchange operator.
12.3.1 The exchange operator

Consider a quantum system that consist of two identical particles (for example
the two electrons in a Helium atom). Let these particles are described by their
corresponding position in space and spin. Suppose particle 1 has spin up and
positioned at a point described by the position vector ~r1 and particle 2 has spin
down and positioned at, ~r2 ; as shown in Fig.12.1 . Using Dirac notation we may
Figure 12.1: Two spin-1/2 particles located at two di¤erent points in space.
12.3. IDENTICAL PARTICLES AND THE EXCHANGE OPERATOR 321
describe each particle 1 state as
jai = jr1 i j+zi ) jai = jr1 ; +zi (12.23)
and particle 2 state as
jbi = jr2 i j zi ) jbi = jr2 ; zi (12.24)
so that the two-particle system state can be written as
ja; bi = jai1 jbi2 : (12.25)
The exchange operator P^12 is de…ned as
P^12 ja; bi = jb; ai = jbi1 jai2 (12.26)
The exchange operator switches the state between the two particles as shown
in Fig. Noting that
Figure 12.2: E¤ect of the exchange operator on a two spin-1/2 particles state.
P^12
2
ja; bi = P^12 jb; ai = jai1 jbi2 = ja; bi (12.27)
we can say that

P^12
2
=I (12.28)
Let’s solve the the eigenvalue equation
P^12 j i = j i (12.29)
for the exchange operator, where j i is a two particle state
j i = jai1 jbi2 = ja; bi : (12.30)
To this end, we note that
ha; bj P^12 ja; bi ha; bj P^12 jb; ai 1 1

= (12.31)
hb; aj P^12 ja; bi hb; aj P^12 jb; ai 2 2
so that applying Eq. (12.26), we …nd
ha; bj b; ai ha; bj a; bi 1 1
= (12.32)
hb; aj b; ai hb; aj a; bi 2 2
From the orthonormality relations for the eigenstates of the two-particle system
we have
ha; bj b; ai = haj1 hbj2 jbi1 jai2 = haj1 jbi1 hbj2 jai2 = 0 (12.33)
ha; bj a; bi = haj1 hbj2 jai1 jbi2 = haj1 jai1 hbj2 jbi2 = 1 (12.34)
This leads to
0 1 1 1
= (12.35)
1 0 2 2
The eigenvalues and the corresponding normalized eigenvectors for this equation
can easily be shown to be
1
j iS = p (ja; bi + jb; ai) ; =1
2
and
1
j iA = p (ja; bi jb; ai) ; = 1;
2
where the subscript S and A refer to symmetric and antisymmetric states
12.3.2 The Pauli principle

The Pauli principle is an important law of nature that symmetry or antisym-
metry under the interchange of two particles is a characteristic of the particles,
and not something that can be arranged in the preparation of the initial state.
This law, which was discovered by Pauli, states that
12.3. IDENTICAL PARTICLES AND THE EXCHANGE OPERATOR 323
(1) Systems consisting of identical particles of half-odd integral spin (i.e., spin
1/2,3/2,...) are described by antisymmetric wave functions. Such particles
are called fermions and are said to obey Fermi-Dirac statistics.
(2) Systems consisting of identical particles of integral spin (0,1,2,....) are de-
scribed by symmetric wave functions. Such particles are called Bosons
and are said to obey Bose-Einstein statistics.
Example 12.1 Consider two photons with same wave length, ; but di¤erent
polarization. Suppose we interfere these two photons using a 50/50 po-
larizing beam splitter as shown in Fig. 12.3Then the momentum of these
Figure 12.3: Interference of two photons using 50/50 polarizing beam splitter.
photons is given by
h h
p~ = x
^; ~q = y^: (12.36)
which we may represent using Dirac notation, as jpi1 and jqi2 for photon
1 and photon 2, respectively. Suppose photon 1 is right polarization jRi1
and photon 2 has left polarization jRi2 : Which of the following state are
the possible two photon state
1 1
j i1 = p (jpi1 jqi2 + jqi1 jpi2 ) p (jRi1 jLi2 jLi1 jRi2 ) ;
2 2
1
j i2 = p (jpi1 jqi2 jqi1 jpi2 ) jRi1 jRi2 ;
2
1 1
j i3 = p (jpi1 jqi2 + jqi1 jpi2 ) p (jRi1 jLi2 + jLi1 jRi2 ) ;
2 2
j i4 = jpi1 jqi2 jRi1 jLi2 ;
1 1
j i5 = p (jpi1 jqi2 jqi1 jpi2 ) p (jRi1 jLi2 jLi1 jRi2 ) :
2 2
Solution: Photons are Bosons and two or more Bosonic particles are described
by a symmetric state. That means for Bosonic multiparticle state, j i ;
we must …nd
P^12 j i = j i : (12.37)
Thus
1 1
P^12 j i1 = p P^12 (jpi1 jqi2 + jqi1 jpi2 ) p (jRi1 jLi2 jLi1 jRi2 )
2 2
1 1
= p (jqi1 jpi2 + jpi1 jqi2 ) p (jLi1 jRi2 jRi1 jLi2 )
2 2
1 1
= p (jpi1 jqi2 + jqi1 jpi2 ) p (jRi1 jLi2 jLi1 jRi2 )
2 2
^
) P12 j i = j i ; (12.38)
1 1
1
P^12 j i2 = p P^12 (jpi1 jqi2 jqi1 jpi2 ) jRi1 jRi2
2
1 1
= p (jqi1 jpi2 p (jpi1 jqi2
jpi1 jqi2 ) jRi1 jRi2 = jqi1 jpi2 ) jRi1 jRi2
2 2
) P^12 j i2 = j i2 (12.39)
1 1
P^12 j i3 = p P^12 (jpi1 jqi2 + jqi1 jpi2 ) p (jRi1 jLi2 + jLi1 jRi2 )
2 2
1 1
= p (jqi1 jpi2 + jpi1 jqi2 ) p (jLi1 jRi2 + jRi1 jLi2 )
2 2
) ^
P12 j i3 = j i3 (12.40)
P^12 j i4 = P^12 jpi1 jqi2 jRi1 jLi2 = jqi1 jpi2 jLi1 jRi2 ) P^12 j i4 6= j i4 ;
(12.41)
12.4. THE HELIUM ATOM–A TWO-FERMION SYSTEM 325
1 1
P^12 j i5 = p P^12 (jpi1 jqi2 jqi1 jpi2 ) p (jRi1 jLi2 jLi1 jRi2 )
2 2
1 1
= p (jqi1 jpi2 jpi1 jqi2 ) p (jLi1 jRi2 jRi1 jLi2 )
2 2
1 1
= p (jpi1 jqi2 jqi1 jpi2 ) p (jRi1 jLi2 jLi1 jRi2 )
2 2
^
) P12 j i5 = j i5 : (12.42)
The above results show that only possible state for the two photons emerg-
ing from the beam splitter are j i3 and j i5 :
Homework problem # 2 : Suppose we replace photon 1 by electron 1 and
photon 2 by electron 2 with the same momentum. We use spin instead of
polarization for electrons so let’s say electron 1 has spin up j+zi and electron 2
has spin down j zi : Suppose the 50/50 polarizing beam splitter is replaced by
a similar device capable of interchanging both the momentum and spin of the
electrons. Write at least …ve states like in Example 12.1 and show that which
of these states are possible two electron state.
Homework problem # 3 : Consider N Fermions that do not interact with each
other but do interact with a common potential in one dimension. Show that
the antisymmetric wave function is given by the so-called Slater determinant
:::
:::
1 :
u (x1 ; x1 ; :::xN ) = p :
N :
:
12.4 The Helium atom–a two-fermion system

The Helium atom is the simplest two-electron atom and yet di¢ cult to obtain
an exact solution to the energy eigenvalue equation. The best approximate solu-
tions close to experimentally measured quantities, such as the ground and …rst
excited state of the electron, are determined using various quantum mechanical
approximation approach. In this section using, perturbative and variational
approach, we will study the energy shift in the ground and excited state in a
Helium atom. Consider a neutral Helium atom with nucleus centered at the
origin and the two electrons positioned at two points described by the position
vectors ~r1 = (r1 ; 1 ; '1 ) and ~r2 = (r2 ; 2 ; '2 ) as shown in the Fig. 12.4. The
distance between the two electrons is
q
j~r1 ~r2 j = r12 + r22 2r1 r2 cos ( ); (12.43)
where
cos ( ) = cos ( 1 ) cos ( 2 ) + sin ( 1 ) sin ( 2 ) cos ('1 '2 ) : (12.44)
Figure 12.4: The Helium atom.
The quantum Hamiltonian describing the helium atom can then be written as
2 2
^ = p^1 + p^2 Ze2 Ze2 e2
H + ; (12.45)
2me 2me 4 0 r1 4 0 r2 4 0 j~
r1 ~r2 j
where the last term is due to the repulsive interaction of the electron. Here
note that we have neglected the small e¤ects due to the motion of the nucleus,
relativistic e¤ ects, spin-orbit coupling, and the e¤ ect of the current caused by
the motion of one electron on the other electron.
12.4.1 Perturbative approach

Suppose the electrons ignore each other and we drop the repulsive interaction
energy. Then the Hamiltonian becomes
^0 = H
H ^ (1) + H (2) ; (12.46)
where
2
^ (i) = pî Ze2
H : (12.47)
2me 4 0 ri
Eq. (12.47) is the sum of the Hamiltonian for two none interacting Hydrogen-
like atoms the eigenvalue equation of which can be written as
^ 0 jEi = E jEi
H (12.48)
or in the position space as
^ (1) + H (2)
H (~r1 ; ~r2 ) = E (~r1 ; ~r2 ) : (12.49)
Since the operators f^

p1 ; ~r1 g and f^p2 ; ~r2 g belong to momentum and position of
two di¤erent electrons, the energy operators commute,
h i
^ (1) ; H (2) = 0:
H (12.50)
This means simultaneous eigenstates can be obtained for H ^ 0; H

^ (1) ; and H (2) : We
^ (1) and H (2) as these operators
have already solved the eigenvalue equation for H
are that of the Hydrogenic atom
^ (i) jn; l; mi = E (i) jn; l; mi :

H (12.51)
i nl i
In position space, we may write
^ (1) (1) (1) (1) ^ (2) (2) (2) (2)

H n;l;m (~r1 ) = Enl n;l;m (~r1 ) ; H n;l;m (~r2 ) = Enl n;l;m (~r2 ) :
(12.52)
so that the eigenvalue equation in position space
^ 0 (~r1 ; ~r2 ) = E (0) (~r1 ; ~r2 )
H (12.53)
gives an eigenstate
(1) (2)
(~r1 ; ~r2 ) = n;l;m (~r1 ) n;l;m (~r2 ) (12.54)
and energy eigenvalue
(1) (2)
E (0) = Enl + Enl : (12.55)
We recall that for Hydrogenic atom
mc2 2 1 13:6
Enl = (Z ) 2 = Z2 ev: (12.56)
2 n n2
In the table below we have computed the energy for the ground and …rst ex-
cited state of a Helium atom obtained using Eq. (12.56) along with the results
obtained using perturbative and variational approach without ignoring the re-
pulsive interaction of the two electrons which we will discuss in the next sections.
State No electron- Perturbative Variational Experimental
electron
interaction
n1 = 1; n2 = 108:8eV 74:8eV 77:4eV 79eV
1
n1 = 1; n2 = 68eV
2
n1 = 2; n2 = 68eV
1
We now include the repulsive interaction of the electron as perturbation and

determine the energy shift for the ground and …rst excited states. To this end,
we note that the Hamiltonian in Eq. (12.45) can be written as
^ =H
H ^ 0 + H1 (12.57)
where
^1 = e2
H : (12.58)
4 0 j~
r1 ~r2 j
The energy shift due to this perturbation in the …rst order is given by
En(1) = h ^ j
n j H1 ni ; (12.59)
where n is the eigenstate for the unperturbed system described by the Hamil-
tonian H^ 0 . Though this system is essentially just a two hydrogen-like atoms,
we must be careful as it made of two identical Fermions since Fermions must
be described by antisymmetric eigenstates. Here when we talk about the eigen-
state, n ; we are referring to the total eigenstates which consist of the spacial,
j n i and two spin–1/2 interacting particles eigenstates j i. We may write this
eigenstate as
j ni = j ni j i (12.60)
where
c (jn; l; mi1 jn0 ; l0 ; m0 i2 jn; l; mi2 jn0 ; l0 ; m0 i1 ) ; Antisymmetric
j ni =
c+ (jn; l; mi1 jn0 ; l0 ; m0 i2 + jn; l; mi2 jn0 ; l0 ; m0 i1 ) ; symmetric
(12.61)
and
8
p1 (j+zi1 j zi2 j+zi2 j zi1 ) ; singlet (Antisymmetric)
>
> 2 9
<
j+zi1 j+zi2 ; =
j i= p1 (j+zi j zi + j+zi j zi ) ;
>
> 1 2 2 1 Triplets(symmetric)
: 2 ;
j zi2 j zi1 :
(12.62)
(i) The ground state: For the ground state since both electrons are described by
n = 1; l = m = 0, for spacial part we have only the symmetric eigenstate which
reduces to
j n i = c+ j1; 0; 0i1 j1; 0; 0i2 (12.63)
and therefore we must chose the antisymmetric singlet state for the spin part
1
j i = p (j+zi1 j zi2 j+zi2 j zi1 ) :
2
Thus the normalized antisymmetric total eigenstate is given by
1
j ni = j1; 0; 0i1 j1; 0; 0i2 p (j+zi1 j zi2 j+zi2 j zi1 ) (12.64)
2
which we may also write as

1
j ni = p (j1; 0; 0; +zi1 j1; 0; 0 zi2 j1; 0; 0 + zi2 j1; 0; 0 zi1 ) : (12.65)
2
The energy shift for the ground state using Eq. (12.64) can then be expressed
as
1 ^ 1 j1; 0; 0i j1; 0; 0i
En(1) = h1; 0; 0j1 h1; 0; 0j2 p (h+zj1 h zj2 h+zj2 h zj1 ) H 1 2
2
1
p (j+zi1 j zi2 j+zi2 j zi1 ) : (12.66)
2
Since
^1 = e2
H : (12.67)
4 0 j~
r1 ~r2 j
is independent of the spin operators (S^1 ; S^2 ); Eq. (12.66) reduces to
e2 1
En(1) = h1; 0; 0j1 h1; 0; 0j2 j1; 0; 0i1 j1; 0; 0i2 : (12.68)
4 0 j~r1 ~r2 j
Using the two completeness relation

Z Z
3 3
(dr1 ) jr1 ; 1 ; '1 i hr1 ; 1 ; '1 j (dr2 ) jr2 ; 2 ; '2 i hr2 ; 2 ; '2 j
Z Z
3 3
= (dr1 ) (dr2 ) jr1 ; 1 ; '1 ; r2 ; 2 ; '2 i hr1 ; 1 ; '1 ; r2 ; 2 ; '2 j ;
where
3
(dri ) = ri2 dri sin ( i ) d i d'i (12.69)
one can write the …rst order correction in position space as
Z Z
e2 3 3 1
En(1) = (dr1 ) (dr2 ) 100 (~r1 ) 100 (~r2 ) 100 (~r1 ) 100 (~r2 ) :
4 0 j~r1 ~r2 j
(12.70)
A physical interpretation of Eq. (12.70) can easily be obtained if we recall the
probability densities for the two electrons is given be
3 3 3 2
~1 (~r1 ) (dr1 ) = (dr1 ) 100 (~r1 ) 100 (~r1 ) = (dr1 ) j 100 (~r1 )j (12.71)
and
3 3 3 2
~2 (~r2 ) (dr2 ) = (dr2 ) 100 (~r2 ) 100 (~r2 ) = (dr2 ) j 100 (~r2 )j : (12.72)
In terms of this densities, we may write Eq. (12.70) as

Z Z
3 1 3 ( e) ~2 (~
r2 )
En(1) = (dr1 ) ( e) ~1 (~r1 ) (dr2 ) : (12.73)
4 0 j~r1 ~r2 j
We note that the probability density times the charge gives the electrical charge
density. Thus Eq. (12.73) can be expressed in terms of the charge densities for
the two electrons as
1 (~r1 ) = e~1 (~r1 ) ; 2 (~r2 ) = e~2 (~r2 )
one can then write

Z " Z #
3
3 1 2 (~r2 ) (dr2 )
En(1) = 1 (~r1 ) (dr1 ) : (12.74)
4 0 j~r1 ~r2 j
From Theo. Phys. III (Sec. 2.5 & 2.8), we recall that the electrostatic potential
at a point described by the position vector ~r1 ; V (~r1 ) due to a static charge with
a charge density, 2 (~r2 ) ; is given by
Z 3
1 2 (~r2 ) (dr2 )
V (~r1 ) = : (12.75)
4 0 j~r1 ~r2 j
We also recall that the electrostatic energy Uel of another charge with charge
density 1 (~r1 ) placed in a region where the electric potential is described by
V (~r1 ) can be determined from
Z
3
En(1) = Uel = 1 (~
r1 ) V (~r1 ) (dr1 ) : (12.76)
Let’s treat the two electrons as a point charge particles and both electrons are
located at two di¤erent points equally distant from the Nucleus. This distance
is the Bohr radius, a0 ; so that one can express the charge densities for each of
these charges as
1 (~r1 ) = e (~r1 ~a1 ) , 2 (~r2 ) = e (~r2 ~a2 ) : (12.77)
where
j~a2 j = j~a2 j = a0 : (12.78)
Then one can easily …nd that
Z " Z #
3
3 1 e (~r2 ~a2 ) (dr2 )
En(1) = e (~r1 ~a1 ) (dr1 )
4 0 j~r1 ~r2 j
2 Z
e (~r1 ~a1 ) 3 e2 1
= (dr1 ) ) En(1) = : (12.79)
4 0 j~r1 ~a2 j 4 0 j~a1 ~a2 j
Therefore, it can easily be seen that the result in Eq. (12.73) for the energy
shift is just the energy shift due to the classical electrostatic interaction energy
of the two electrons.
To determine the exact value we need to evaluate the integral in Eq. (12.70).
To evaluate this integral and also the resulting integrals for the excited states, we
will …rst derive a more general case that is a function of the quantum numbers,
1
hn1 l1 m1 j1 hn2 l2 m2 j2 jn01 l10 m01 i1 jn02 l20 m02 i2
j~r1 ~r2 j
Z Z
3 3 1
= (dr1 ) (dr2 ) n1 l1 m1 (~r1 ) n2 l2 m2 (~r2 ) n01 l10 m01 (~r1 ) n02 l20 m02 (~r2 ) :
j~r1 ~r2 j
(12.80)
From Theo. Phys. II (Section 12.9), we recall that the Inverse-Distance between
the two points shown in Fig. ?? can be expressed as
X1 l X1 l l
X
1 r< 4 r< 0
= P l (cos ) = Ylm ( ; ') Ylm ; '0 ;
j~r ~r0 j rl+1
l=0 > l=0
l+1
2l + 1 r>
m= l
(12.81)
where (
l r 0l
r< r l+1
; r > r0
l+1
= rl
; (12.82)
r> r 0l+1
; r < r0
0 0
cos ( ) = cos ( ) cos + sin ( ) sin cos (' '0 ) ; (12.83)
and the spherical Harmonics satisfy the orthonormality relation

Z Z 2
0 0 0 0 0
Ylm ; '0 Yl0 m0 ; '0 = Ylm ; '0 Yl0 m0 ; '0 sin d 0 d'0
=0 '=0
= ll0 mm0 (12.84)
We now proceed to …nd a general expression for the integral in Eq. (12.80). To
this end, we note that
1
hn1 ; l1 ; m1 j1 hn2 ; l2 ; m2 j2 jn0 ; l0 ; m0 i jn0 ; l0 ; m0 i
~r2 j 1 1 1 1 2 2 2 2
j~r1
Z Z
3 3 n1 l1 m1 (~
r1 ) n2 l2 m2 (~r2 ) n01 l10 m01 (~r1 ) n02 l20 m02 (~r2 )
= (dr1 ) (dr2 ) (12.85)
j~r1 ~r2 j
so that using
3
nlm (~r) = Rnl (r) Ylm ( ; ') ; (dri ) = ri2 dri sin ( i ) d i d'i ; (12.86)
we may write
e2 1
En(1) = hn1 ; l1 ; m1 j1 hn2 ; l2 ; m2 j2 jn01 ; l10 ; m01 i1 jn02 ; l20 ; m02 i2
4 0 j~r1 ~r2 j
1 l
e2 X X 1
) En(1) = (l) 1 (l; m) 2 (l; m) ; (12.87)
0 2l + 1
l=0 m= l
where
Z (Z
1 r1
r2l+2
(l) = Rn1 l1 (r1 ) Rn01 l10 (r1 ) r12 dr1 Rn l (r2 ) Rn02 l20 (r2 ) dr2
0 0 r1l+1 2 2
Z 1
r1l
+ Rn2 l2 (r2 ) Rn02 l20 (r2 ) dr2
r1 r2l 1
Z Z 2
1 (l; m) = sin ( 1 ) d 1 d'1 Yl1 m1 ( 1 ; '1 ) Yl10 m01 ( 1 ; '1 ) Ylm ( 1 ; '1 )
0 0
Z Z 2
2 (l; m) = sin ( 2 ) d 2 d'2 Ylm ( 2 ; '2 ) Yl20 m02 ( 2 ; '2 ) Yl2 m2 ( 2 ; '2 )
0 0
(12.88)
where we splitted the second integral for (l) into r2 < r1 and r2 > r1 ; such
that 8 l
l
r< < rl+12
; r2 < r1
r1
= l : (12.89)
l+1
r> : rl+11
; r2 > r1
r 2
For the ground state (n1 = n2 = 1; l1 = l2 = m1 = m2 = 0; l10 = l20 = m01 =
m02 = 0), using Eq. (12.88), we have

Z 1 (Z
r1
2 r2l+2 2
(l) = jR10 (r1 )j r1 dr1 jR10 (r1 )j dr2
0 0 r1l+1
Z 1
r1l 2
+ jR10 (r1 )j dr2
r1 r2l 1
Z Z 2
1 (l; m) = sin ( 1 ) d 1 d'1 Y00 ( 1 ; '1 ) Y00 ( 1 ; '1 ) Ylm ( 1 ; '1 )
0 0
Z Z 2
2 (l; m) = sin ( 2 ) d 2 d'2 Ylm ( 2 ; '2 ) Y00 ( 2 ; '2 ) Y00 ( 2 ; '2 ) (12.90)
0 0
so that using
1
Y00 ( 2 ; '2 ) = Y00 ( 1 ; '1 ) = p ; (12.91)
4
and the othonormality relation for the spherical Harmonics, we …nd
Z Z 2
sin ( 2 ) d 2 d'2 Ylm ( 2 ; '2 ) Y00 ( 2 ; '2 ) = l0 m0 (12.92)
0 0
one …nds
1
(l; m) = p 1
l0 m0 (l; m) = 2 (12.93)
4
Thus using Eq. (12.87) one can write for the ground state
1 l
e2 X X 1 2 e2
En(1) = (l) ( l0 m0 ) = (0) (12.94)
4 0 2l + 1 4 0
l=0 m= l
Thus the energy shift in Eq. (12.94), becomes

Z
(1) 4e2 1 Z 3 2Zr1
En = 3 exp r12
0 0 a0 a0
Z r1 3 Z 1 3
1 Z 2Zr2 Z 2Zr2
exp r22 dr2 + 3 exp r2 dr2 dr1
r1 0 a30 a0 r1 a0 a0
(12.95)
so that upon carrying out the integration using mathematica
we …nd
e2 5 Z e2 5 Z 5 1 2
En(1) = = = Z mc 2
: (12.96)
0 32 a0 4 0 8 a0 4 2
For a Helium atom, Z = 2
5
En(1) = 2 (13:6eV ) = 34eV (12.97)
4
and
mc2 2 1 Z 2 13:6ev
En = (Z ) 2 = = 54 ) En(0) = 108:8eV: (12.98)
2 n n2
so that
E = En(0) + En(1) = 74:8eV (12.99)
This is the energy of the electron in a Helium atom that is in the ground state
which is close to the experimentally measured value given on Table 1.
(i) The …rst excited state:The Helium atom in the …rst excited state would
have the …rst electron at the energy level,
n = 1 ) l = 0 ) m = 0 ) jn; l; mi = j1; 0; 0i (12.100)
and the second electron at the energy level

l = 0; m=0
n=2) ) jn; l; mi = j2; l0 ; m0 i (12.101)
l = 1; m = 1; 0; 1
or vise versa. This means the spacial part of the eigenstate for the Helium atom
from Eq. (12.61) can be expressed
(
p1 (j1; 0; 0i j2; l0 ; m0 i j1; 0; 0i2 j2; l0 ; m0 i1 ) ; Antisymmetric
2 1 2
j ni = p1 (j1; 0; 0i j2; l0 ; m0 i + j1; 0; 0i j2; l0 ; m0 i ) :
2 1 2 2 1 symmetric
(12.102)
Note that we did not consider

j1; 0; 0i1 j2; l0 ; m0 i2 ; j1; 0; 0i2 j2; l0 ; m0 i1
as these states are neither symmetric nor antisymmetric. Since the total eigen-
state for the two electrons must be antisymmetric, the allowed energy eigenstates
can be spacial symmetric and spin antisymmetric or vise versa. Thus we may
write
1
= p1 (j1; 0; 0i1 j2; l0 ; m0 i2 + j1; 0; 0i2 j2; l0 ; m0 i1 ) j
n 2 1i ;
2
= p1 (j1; 0; 0i1 j2; l0 ; m0 i2 j1; 0; 0i2 j2; l0 ; m0 i1 ) j
n 2 2i ;
3 p1
(12.103)
n = 2
(j1; 0; 0i1 j2; l0 ; m0 i2 j1; 0; 0i2 j2; l0 ; m0 i1 ) j 3i ;
4
= p1 (j1; 0; 0i1 j2; l0 ; m0 i2 j1; 0; 0i2 j2; l0 ; m0 i1 ) j
n 2 4i :
where
j p1
1i = 2
(j+zi1 j zi2 j+zi2 j zi1 ) ; singlet (Antisymmetric) (12.104)
and
9
j 2i = j+zi1 j+zi2 ; =
j p1 (j+zi j zi + j+zi j zi ) ;
3i = 2 1 2 2 1 Triplets(symmetric) (12.105)
;
j 4 i = j zi2 j zi1 :
Then the energy shift which is given by
(1) i ^1 i
Eni = n H n (12.106)
becomes
(1) 1
En1 = p (h1; 0; 0j1 h2; l0 ; m0 j2 + h1; 0; 0j2 h2; l0 ; m0 j1 ) h 1 j
2
H^ 1 p1 (j1; 0; 0i j2; l0 ; m0 i + j1; 0; 0i j2; l0 ; m0 i ) j 1 i ; (12.107)
1 2 2 1
2
(1) 1
En2 = p (h1; 0; 0j1 h2; l0 ; m0 j2 h1; 0; 0j2 h2; l0 ; m0 j1 ) h 2 j
2
H^ 1 p1 (j1; 0; 0i j2; l0 ; m0 i j1; 0; 0i2 j2; l0 ; m0 i1 ) j 2 i ; (12.108)
1 2
2
(1) 1
2
H^ 1 p1 (j1; 0; 0i j2; l0 ; m0 i j1; 0; 0i2 j2; l0 ; m0 i1 ) j 3 i ; (12.109)
1 2
2
(1) 1
2
H^ 1 p1 (j1; 0; 0i j2; l0 ; m0 i j1; 0; 0i2 j2; l0 ; m0 i1 ) j 4 i : (12.110)
1 2
2
We recall one more time that H ^ 1 in Eq. (12.67) is independent of the spin
^ ^
operators (S1 ; S2 ); that means
h i
^ 1 ; S^1 + S^2 = 0:
H
As a result the above four equations reduces to two equations which we may
express as
(1) 1
En1 = p (h1; 0; 0j1 h2; l0 ; m0 j2 + h1; 0; 0j2 h2; l0 ; m0 j1 )
2
H^ 1 p1 (j1; 0; 0i j2; l0 ; m0 i + j1; 0; 0i j2; l0 ; m0 i ) ;
1 2 2 1
2
(1) (1) (1) 1
En2 = En3 = En4 = p (h1; 0; 0j1 h2; l0 ; m0 j2 h1; 0; 0j2 h2; l0 ; m0 j1 )
2
1
^ 1 p (j1; 0; 0i j2; l0 ; m0 i
H 1 2 j1; 0; 0i2 j2; l0 ; m0 i1 ) ; (12.111)
2
which we may rewrite the two equations as
(1) 1n ^ 1 j1; 0; 0i j2; l0 ; m0 i
En = h1; 0; 0j1 h2; l0 ; m0 j2 H 1 2
2
^ 1 j1; 0; 0i j2; l0 ; m0 i
+ h1; 0; 0j2 h2; l0 ; m0 j1 H 2 1
0 0 ^ 0
h1; 0; 0j1 h2; l ; m j2 H1 j1; 0; 0i2 j2; l ; m i1 0
o
h1; 0; 0j2 h2; l; mj1 H ^ 1 j1; 0; 0i j2; l; mi ; (12.112)
1 2
^y = H
Taking into account that the Hamiltonian is a Hermitian operator (H ^ 1 );
1
we have
^ 1 j1; 0; 0i j2; l0 ; m0 i
h2; l0 ; m0 j1 h1; 0; 0j2 H 1 2
0 0 ^ 0
= h2; l ; m j2 h1; 0; 0j1 H1 j1; 0; 0i2 j2; l ; m i10
(12.113)
so that
(1) 1n ^ 1 j1; 0; 0i j2; l0 ; m0 i
En = h2; l0 ; m0 j2 h1; 0; 0j1 H 1 2
2
0 0
+ h2; l ; m j1 h1; 0; 0j2 H ^ 1 j1; 0; 0i j2; l ; m i
0 0
2 1
o
0 0 ^ 0
2 h2; l ; m j2 h1; 0; 0j1 H1 j1; 0; 0i2 j2; l ; m i1 0
(1)
) En = : (12.114)
where
e2 1
= h2; l0 ; m0 j2 h1; 0; 0j1 j1; 0; 0i1 j2; l0 ; m0 i2
4 0 j~r1 ~r2 j
e2 1
= h2; l0 ; m0 j1 h1; 0; 0j2 j1; 0; 0i2 j2; l0 ; m0 i1 (12.115)
4 0 j~r1 ~r2 j
e2 1
= h2; l0 ; m0 j2 h1; 0; 0j1 j1; 0; 0i2 j2; l0 ; m0 i1 (12.116)
4 0 j~r1 ~r2 j
We can determine the values for these equations following the same approach
we used for the ground state. Recalling that for the …rst excited state;
l0 = 0; m0 = 0
n=2) (12.117)
l0 = 1; 0
m = 1; 0; 1
However, since Lz commutes with the total Hamiltonian (or the interaction
Hamiltonian), it is a constant of motion and therefore it is independent of time.
Thus this means the result for m0 = 0 is the same as for m0 = 1; 1 and we
can …nd only the values for m0 = 0 when l0 = 1 in Eqs. (12.115) and (12.116).
Thus, applying the relation in Eqs. (12.87) and (12.88), one can write for
l0 = 0; m0 = 0;
e2 1
= h2; 0; 0j2 h1; 0; 0j1 j1; 0; 0i1 j2; 0; 0i2
4 0 j~r1 ~r2 j
1 l
e2 X X 1
= (l) 1 (l; m) 2 (l; m) (12.118)
0 2l0 + 1
l=0 m= l
where
Z (Z 0
1 r1
2 r2l +2 2
(l) = jR10 (r1 )j r12 dr1 0 jR20 (r2 )j dr2
0 0 r1l +1
Z 0
)
1
r1l 2
+ l0 1
jR20 (r2 )j dr2 ;
r1 r2
Z Z 2
1 (l; m) = sin ( 1 ) d 1 d'1 Y00 ( 1 ; '1 ) Y00 ( 1 ; '1 ) Ylm ( 1 ; '1 )
0 0
Z Z 2
2 (l; m) = sin ( 2 ) d 2 d'2 Ylm ( 2 ; '2 ) Y00 ( 2 ; '2 ) Y00 ( 2 ; '2 )
0 0
(12.119)
and
e2 1
= h2; 0; 0j2 h1; 0; 0j1 j1; 0; 0i2 j2; 0; 0i1
4 0 j~r1 ~r2 j
1 l
e2 X X 1 0 0 0
= (l) 1 (l; m) 2 (l; m) (12.120)
0 2l + 1
l=0 m= l
where
Z (Z
1 r1
0 r2l+2
(l) = R10 (r1 ) R20 (r1 ) r12 dr1 R20 (r2 ) R10 (r2 ) dr2
0 0 r1l+1
Z 1
r1l
+ R20 (r2 ) R10 (r2 ) dr2
r1 r2l 1
Z Z 2
0
1 (l; m) = sin ( 1 ) d 1 d'1 Y00 ( 1 ; '1 ) Y00 ( 1 ; '1 ) Ylm ( 1 ; '1 ) ;
0 0
Z Z 2
0
2 (l; m) = sin ( 2 ) d 2 d'2 Ylm ( 2 ; '2 ) Y00 ( 2 ; '2 ) Y00 ( 2 ; '2 ) :
0 0
(12.121)
Noting that
0 0 1
1 (l; m) = 2 (l; m) = 1 (l; m) = 2 (l; m) = p l0 m0 (12.122)
4
one …nds
1 l
e2 X X 1 2 e2
= (l) ( l0 m0 ) = (0) ;
4 0 2l + 1 4 0
l=0 m= l
1 l
e2 X X 1 0 2 e2 0
= (l) ( l0 m0 ) = (0) (12.123)
4 0 2l + 1 4 0
l=0 m= l
The energy correction

(1)
En =
where
Z 1 Z r1
e2 2 1 2
= jR10 (r1 )j r12 dr1 jR20 (r2 )j r22 dr2
4 0 0 r1 0
Z 1
2
+ jR20 (r2 )j r2 dr2
r1
2 Z 1 Z r1
e 1
= R10 (r1 ) R20 (r1 ) r12 dr1 R20 (r2 ) R10 (r2 ) r22 dr2
4 0 0 r1 0
Z 1
+ R20 (r2 ) R10 (r2 ) r2 dr2 (12.124)
r1
Similarly, l0 = 1; and m0 = 0; we …nd

e2 1
= h2; 1; 0j2 h1; 0; 0j1 j1; 0; 0i1 j2; 1; 0i2
4 0 j~r1 ~r2 j
1 l
e2 X X 1
= (l) 1 (l; m) 2 (l; m) ; (12.125)
0 2l + 1
l=0 m= l
where
Z (Z
1 r1
2 r2l+2 2
(l) = jR10 (r1 )j r12 dr1 jR21 (r2 )j dr2
0 0 r1l+1
Z 1
r1l 2
+ jR21 (r2 )j dr2
r1 r2l 1
Z Z 2
1 (l; m) = sin ( 1 ) d 1 d'1 Y00 ( 1 ; '1 ) Y00 ( 1 ; '1 ) Ylm ( 1 ; '1 )
0 0
Z Z 2
2 (l; m) = sin ( 2 ) d 2 d'2 Ylm ( 2 ; '2 ) Y10 ( 2 ; '2 ) Y10 ( 2 ; '2 )
0 0
(12.126)
and
1
= h2; 1; 0j2 h1; 0; 0j1 j1; 0; 0i2 j2; 1; 0i1
j~r1 ~r2 j
1 l
e2 X X 1 0 0 0
= (l) 1 (l; m) 2 (l; m) (12.127)
0 2l + 1
l=0 m= l
where
Z (Z
1 r1
0 r2l+2
(l) = R10 (r1 ) R21 (r1 ) r12 dr1 R21 (r2 ) R10 (r2 ) dr2
0 0 r1l+1
Z 1
r1l
+ R21 (r2 ) R10 (r2 ) dr2
r1 r2l 1
Z Z 2
0
1 (l; m) = sin ( 1 ) d 1 d'1 Y00 ( 1 ; '1 ) Y10 ( 1 ; '1 ) Ylm ( 1 ; '1 )
0 0
Z Z 2
0
2 (l; m) = sin ( 2 ) d 2 d'2 Ylm ( 2 ; '2 ) Y00 ( 2 ; '2 ) Y10 ( 2 ; '2 )
0 0
(12.128)
Noting that
1 1
Y00 ( ; ') = p ; Y10 ( ; ') = Y10 ( ; ') = p P1 (cos ) ; (12.129)
4 4
where we used that for m = 0 the spherical harmonics given by
s
m 2l + 1 (l m)! m
Ylm ( ; ') = ( 1) P (cos ) eim' ; (12.130)
4 (l + m)! l
reduces to
1
Yl0 ( ; ') = Yl0 ( ; ') = p Pl (cos ) ; (12.131)
4
we have
1 0 0 1
1 (l; m) = p l0 m0 ; 2 (l; m) = 2 (l; m) = p l1 m0 (12.132)
4 4
so that for one …nds
1 X
X l
e2 1 e2
=p (l) 2 (l; m) l0 m0 =p (0) 2 (0; 0)
4 0 l=0 m= l 2l + 1 4 0
2
e
) = (0) ;
4 0
1 l
e2 X X 1 0 2 e2 0
= (l) ( l1 m0 ) = (0) ; (12.133)
4 0 2l + 1 4 0
l=0 m= l
where we used
Z Z 2
2 (0; 0) = sin ( 2 ) d 2 d'2 Y00 ( 2 ; '2 ) Y10 ( 2 ; '2 ) Y10 ( 2 ; '2 )
0 0
Z Z 2
1 1
=p sin ( 2 ) d 2 d'2 Y10 ( 2 ; '2 ) Y10 ( 2 ; '2 ) = p (12.134)
4 0 0 4
Therefore, one …nds for the energy correction when l0 = 1; m0 = 0
(1) e2 0
En = = [ (0) (0)] ; (12.135)
4 0
where
Z 1 Z r1
e2 2 1 2
= jR10 (r1 )j r12 dr1 jR21 (r2 )j r23 dr2
4 0 0 r12 0
Z 1
2
+r1 jR21 (r2 )j dr2 (12.136)
r1
2 Z 1 Z r1
e 1
= R10 (r1 ) R21 (r1 ) r12 dr1 R21 (r2 ) R10 (r2 ) r23 dr2
4 0 0 r12 0
Z 1
+r1 R21 (r2 ) R10 (r2 ) dr2 : (12.137)
r1
It is standard to express these energy values using l0 = 0 = s; l0 = 1 = p; l0 = 2

notations. Noting that
n = 2; l0 = 0 ! 2s; n = 2; l0 = 1 ! 2p; n = 1; l0 = 0 ! 1s;
when one of the electron is in the 2s state the other electron is going to be in
the 1s state and the energy correction
(1)
E1s;2s = = 11:4eV 1:2eV: (12.138)
where and are given by Eq. (12.124). The other possible state is when one
electron is in a 2p state and the other electron is going to be in the 1s state and
the energy is given by
(1)
E1s;2p = = 13:2eV 0:9eV: (12.139)
where and are given by Eq. (12.137).

The result for as one can easily see from Eqs. (12.124) or (12.137) it is just
an electrostatic interaction of the two electrons like what we saw for the ground
state. However, the result for is pure quantum mechanical result. There
is no classical interpretation that we can assign to this term. Its origin lies in
the Pauli principle, and its sign depends on whether the state has spin 0 or 1.
Thus , because of this exchange contribution, the singlet and triplet terms are no
longer degenerate. For the triplet state with spin 1; the spacial wave function
is antisymmetric n1 l1 m1 (~
r1 ) n2 l2 m2 (~
r2 ) . This means the probability of
the electrons to be found close to one another is relatively small compared to
when the spacial wave function is symmetric n1 l1 m1 (~
r1 ) + n2 l2 m2 (~r2 ) for
the singlet case where the total spin is zero which means the two electrons posses
opposite spin. So the electrons are somewhat constrained to stay away from each
other for the triplet state. This tends to reduce the screening e¤ect, so that each
electron "sees" more of the nuclear charge and it also tends to make the repulsion
between the electrons less e¤ective than the spacial symmetric singlet state.
Homework: Show that the expressions for in Eqs. (12.124) or (12.137)
describe a simple electrostatic interaction energy of two electrons.
Homework: Find the total energy for each energy levels for the two electrons
in the Helium atom and based on the discussion we made earlier identify the
singlet and triplet energy values.
12.4.2 Variational approach

We were introduced to the calculus of variation Theo.Phys. I (Sec 9.1-9.5).
In fact we used the calculus of variation to solve the famous Brachystochrone
Problem and also to prove that the shortest distance between two points is
the distance measured along a straight line. In either case we were able to
solve the problems by introducing a variational parameter and minimizing the
relevant quantity (time in the …rst and distance in the second) with respect to
this variational parameter. Here we will determine the ground state energy of
the Helium atom using calculus of variation following a similar approach. We
…rst introduce a variational parameter, minimize the energy with respect to
this variational parameter, and use the result to …nd the ground state energy.
To this end, we …rst want to show that the energy is indeed a minimum for
the right value of the variational parameter. We consider a Hamiltonian H ^
and an arbitrary square integrable trial state vector, j i ; which we chose to be
normalized
h j i = 1: (12.140)
This state can be expresses as linear superposition of the complete eigenstates

of this Hamiltonian as
X X
j i= jEn i hEn j i = cn jEn i ; (12.141)
n n
where
^ jEn i = En jEn i :
H (12.142)
is the exact eigenvalue equation of the system. The expectation value for the
energy can then be expressed as
XX XX
h jH^j i = ^ jEn i =
cn cm hEm j H cn cm En hEm jEn i
m n m n
X 2
) ^j i=
h jH jcn j En ; (12.143)
n
where we used the orthonormality of the energy eigenstates,

hEm jEn i = mn : (12.144)
From the normalization of the state vector, we have
X 2
h j i= jcn j = 1; (12.145)
n
so that for E0 ; which is the lowest energy, we can write

X X
jcn j En =
^j i= 2 2
h jH jcn j E0 : (12.146)
n n
This shows that

^ j i = E0 :
h jH (12.147)
We can determine the closest value to E0 from the expectation value for the
^ j i using an arbitrary state j i that is function of
ground state energy h j H
variational parameters 1 ; 2 ; 3 :::: All we need to do is chose the state properly
so that we can make our life easy and minimize the expectation value with
respect to these parameters. This means for the properly chosen state vector
j i=j ( 1; 2; 3 :::)i (12.148)
for the expectation value we set
@ ^j (
h ( 1; 2; 3 :::)j H 1; 2; 3 :::)i = 0: (12.149)
@ i
for i = 1; 2; 3::: so that the energy would take a minimum value close to E0 :
For the Helium atom we chose the atomic number as our variational para-
meter, 1 = Z; ~ and the state vector be that of two Hydrogenic atoms. Thus for
the ground state we may write the state vector
E E E E
j i= Z~ Z~ = 1; 0; 0 Z~ 1; 0; 0 Z~ ; (12.150)
1 2 1 2
where !
p^2i ~ 2
Ze ~i j i
j i=E (12.151)
2me 4 0 ri
and
me c2 ~ 2
~i =
E Z : (12.152)
2
Noting that in the position space we can write the state vector using the com-
pleteness relation for position eigenstate as
E E
(~r1 ; ~r2 ) = hr1 ; r2 j i = hr1 1; 0; 0 Z~ hr2 1; 0; 0 Z~
1 2
= 100 (~r1 ) 100 (~r2 ) = R10 r1 Z~ Y00 ( 1 ; '1 ) R10 r2 Z~ Y00 ( 2 ; '2 )
(12.153)
1
= R10 r1 Z~ R10 r2 Z~ ; (12.154)
4
where we used
1
Y00 ( ; ') = p :
4
Using the explicit form for the radial part of the ground state, the wave function
can be expressed
! 23 ! ! 32 !
Z~ ~ 1
Zr Z~ ~ 2
Zr
(r1 ; r2 ) = 2 exp 2 exp :
a0 a0 a0 a0
Now recalling that for a Helium atom the Hamiltonian is

2 2
^ = p^1 + p^2 Ze2 Ze2 e2
H + ; (12.155)
2me 2me 4 0 r1 4 0 r2 4 0 j~
r1 ~r2 j
which we may rewrite in terms of the variational parameter Z~ as
2 ~ 2 p^2 ~ 2 Z Z~ e2 Z Z~ e2
^ = p^1
H
Ze
+ 2
Ze
2me 4 0 r1 2me 4 0 r2 4 0 r1 4 0 r2
e2
+ : (12.156)
4 0 j~r1 ~r2 j
or
^ =H
H ^1 + H
^2 + H
^ 3; (12.157)
where
!
2
X p^2i ~ 2
Ze
2
X Z Z~ e2 e2
^1 =
H ^2 =
;H ^3 =
;H
i=1
2me 4 0 ri i=1
4 0 ri 4 0 j~
r1 ~r2 j
(12.158)
Then the expectation value of this Hamiltonian becomes

^ j i = h jH
h jH ^1 j i + h j H
^2 j i + h j H
^3 j i : (12.159)
Applying the relation in Eq. (12.151), we …nd for the …rst term
D D E E
h jH^1 j i = 1; 0; 0 Z~ 1; 0; 0 Z~ H^ 1 1; 0; 0 Z~ 1; 0; 0 Z~
1 2 1 2
2
) ^ 1 j i = 2E
h jH ~i = me c 2
Z~ : (12.160)
For the second term, we have

^2 j i
h jH
2 Z Z~ e2 D D 1 E E
= 1; 0; 0 Z~ 1; 0; 0 Z~ 1; 0; 0 Z~ 1; 0; 0 Z~
4 0 1 2 r2 1 2
! 23 !2
8 Z Z~ e2 Z 1
Z~ ~ 1
Zr
= exp r12 dr1
0 0 a0 a0
Z ! 32 ! 2
1
Z~ ~ 2
Zr
exp r2 dr2 (12.161)
0 a0 a0
Upon carrying out the integration, one …nds
e2 Z Z~ Z~
^2 j i =
h jH (12.162)
2 0 a0
or using
~
a0 = ; e2 = 4 0 ~c (12.163)
me c
we may write
^2 j i =
h jH 2me c2 2
Z Z~ Z:
~ (12.164)
We have already calculated the resulting integral for the third term in Eq.
~
(12.159). The result can be obtained from Eq. (12.96) by replacing Z with Z;
^3 j i
h jH
e2 D D 1 E E
= 1; 0; 0 Z~ 1; 0; 0 Z~ 1; 0; 0 Z~ 1; 0; 0 Z~
4 0 1 2 j~r1 ~r2 j 1 2
^ 3 j i = 5 Z~
) h jH
1 2
mc 2
: (12.165)
4 2
Therefore the expectation value in Eq. (12.159) becomes
^j i= 5~
h jH me c2 2
2Z Z~ Z~ 2 Z : (12.166)
8
Now we minimize this expectation value with respect to the variational para-
meter
@ ^ j i = 0 ) 4Z~ + 4Z 5 = 0 ) Z~ = Z 5
h jH : (12.167)
@Z~ 4 16
Substituting Z = 2 for a Helium atom we …nd
5
Z~ = Z= 1:68 (12.168)
16
The ground state energy in Eq. (??) will then be
^j i=
E0 = h j H 77:38eV: (12.169)
This result is much better than what we obtained using perturbation approach.
It is close to the experimental result, E0 = 79eV:
For the excited state we use a similar approach. But we must be careful with
choosing our trial state vector. For example the trial state vector for the …rst
exited state must be orthogonal to the energy eigenstate for the ground state,
and also must be normalized as all state vectors need to be normalized: What
this mean is that if our trial state vector for the …rst excited state is j 1 i and
j i is the arbitrary square integrable trial state vector, then
hE0 j 1i = 0; h 1 j 1i =1 (12.170)
To …nd this trial state vector, we use Gram-Schmidt orthogonalization method
that we were introduced in Theo. Phys. I (Sec. 4.10). The only di¤erence is
that here we do the orthogonalization in Hilbert space instead of a vector space.
Our unit vectors in Hilbert space are the energy eigenstates. Then Applying
this technique, we may express the trial state vector for the …rst excited state
as
j 1 i = C1 (j i hE0 j i jE0 i) ;
where E0 (jE0 i) is the energy eigenvalue (eigenstate) for the ground state and
j i is given be Eq. (12.141). The trial state vector must also be normalized
2
h 1 j 1i
= 1 = jC1 j (h j hE0 j i hE0 j) (j i hE0 j i jE0 i)
h i
2 2 2
) jC1 j h j i jhE0 j ij + h j i jhE0 j ij hE0 j E0 i = 1
1
) C1 = r ; (12.171)
2
2 1 jhE0 j ij
where we used
hE0 j E0 i = 1 = h j i
Then the trial state vector can be expressed as
j i hE0 j i jE0 i
j 1i =r : (12.172)
2
2 1 jhE0 j ij
For higher excited state we follow the same procedure.

Chapter 13
Quantum …eld theory
In this chapter we get introduced to the quantum description of the free elec-
tromagnetic waves. Using the quantum description of an EM wave we will
also study the interaction of photons with an atom. In our study of both the
single electron hydrogen and multielectron helium atoms so far we have consid-
ered these atoms isolated and not interacting with any external electromagnetic
…elds. When these atoms interact with an electromagnetic radiation, the Hamil-
tonian becomes time dependent. In such cases we need to use time-dependent
perturbation theory. We begin this chapter with time dependent perturbation
theory.
13.1 Time dependent perturbation theory

As in the case of the time independent perturbation theory, we begin with the
unperturbed system for which we know the solution for the eigenvalue equation
^0 j (0)
H ki = Ek j ni ; (13.1)
the energy eigenstates form a complete set of an orthonormal vectors,
1
X
j ki h kj = I:
k
Suppose the system is subjected to some interaction which we may describe by

a time dependent Hamiltonian, H ^ 1 (t) : Then the total Hamiltonian, H;
^ can be
expressed as
H^ (t) = H ^0 + H ^ 1 (t) ; (13.2)
where is the same parameter we introduced in the time independent perturba-
tion theory which we will set = 1. Since now the Hamiltonian is explicitly time
dependent we must use the time-dependent Shöudinger equation (Shöudinger
picture)
d ^ (t) j ^0 + H
^ 1 (t) j
i~ j n (t; )i = H n (t; )i = H n (t; )i : (13.3)
dt
345
346 CHAPTER 13. QUANTUM FIELD THEORY
For the unperturbed system ( = 0), where H^ (t) = H

^ 0 ; the state must reduce
to
j n (t; )i = 0n (t) ; (13.4)
0
where n (t) ;which also satis…es the Shöudinger equation
d 0 ^0 0
i~ n (t) = H n (t) ; (13.5)
dt
is the state vector for the unperturbed system. If the unperturbed system is
initially in a state
0
n (0) = j n i (13.6)
we recall that, at a latter time, t;the state vector for the unperturbed system
can be expressed as
^ t
1
X ^ t
1
X ^ t
H0 H 0 H0
0 i i i
n (t) = e ~ j ni = e ~ j ki h kj ni = e ~ j k i kn
k k
(0)
En t
0 i
) n (t) = e ~ j ni ; (13.7)
where j n i is the initial state of the unperturbed system. Since the energy eigen
vectors form a complete set, we can express the state vector for the perturbed
system, j n (t)i ; as a linear superposition of the eigenstates for the unperturbed
energy eigenstates, j k i ;
1
X 1
X
j n (t; )i = j ki h kj n (t; )i = fnk (t; ) j ki ; (13.8)
k k
where for = 0; we must …nd

(0)
En t
i
fnk (t; ) = e ~ : (13.9)
This suggests that one can express

(0)
E t
i k
fnk (t; ) = Cnk (t; ) e ~ ; (13.10)
with the condition for = 0;

(0)
En t
i
fnk (t; ) = e ~ ) Cnk (t = 0; = 0) = 1 (13.11)
Thus the state vector for the Hamiltonian

^ (t) = H
H ^0 + H
^ 1 (t) ; (13.12)
can be expressed as
1
X E
(0)
t
i k
j n (t; )i = Cnk (t; ) e ~ j ki (13.13)
k
13.1. TIME DEPENDENT PERTURBATION THEORY 347
Now let’s isolate the term, k = n; (the initial state for the unperturbed system)
from the summation so that we can write
(0) 1
X E
(0)
t
En t k
i i
j n (t; )i = Cnn (t; ) e ~ j ni + Cnk (t; ) e ~ j ki (13.14)
k6=n

2 3
(0) 1
X E
(0)
t
E t
i n~ i k~
j n (t; )i = N ( ) 4Cnn (t; ) e j ni + Cnk (t; ) e j ki
5
k6=n
(13.15)
The factor N ( ) is determined from the othonormalization condition
h m (t; ) j n (t; )i = mn : (13.16)
and therefore we have the freedom to chose the phase of j n (t)i ; (or in other
words, N ( )): We can then chose this phase so that we can set Cnn (t; ) = 1
and we write Eq. (13.15) as
2 3
(0) X1 E
(0)
t
En t k
j n (t; )i = N ( ) 4e i ~ j n i + Cnk (t; ) e i ~ j k i5 : (13.17)
k6=n
Note that since this state must reduce to the initial state, j ni ; for the unper-
turbed system ( ! 0; t = 0), we must have
N ( = 0) = 1 and Cnk (t = 0; = 0) = 0; for k 6= n; (13.18)
this means
0
j n (t = 0; = 0)i = n (t = 0) = j ni : (13.19)
Taking this into consideration, we can then express the expansion coe¢ cients
Cnk (t; ) for k 6= n as
(1) 2 (2) 3 (3)
Cnk (t; ) = Cnk (t) + Cnk (t) + Cnk (t) + ::: (13.20)
Based on the same argument, since we are expecting the energy for the perturbed
system must reduce to the energy of the unperturbed system En0 in the absence
of perturbation (interaction) (i.e. ! 0; t ! 0). Therefore, we may express
^ (t) = H
H ^ (1) (t) +
^0 + H 2 ^ (2) (t) +
H 3 ^ (3) (t) + :::
H (13.21)
1 1 1
^n ; H (1)
^n ; H (2) (3)
^ n ... are 1st , 2nd , 3rd ..order corrections due to the perturb-
where H
ing Hamiltonian H ^1
First order time dependent perturbation theory: In the …rst order time de-
pendent perturbation theory we keep the terms up to the …rst order of ; so
that
(1)
Cnk (t; ) = Cnk (t) (13.22)
and
^ (t) = H
H ^ (1) (t) :
^0 + H (13.23)
1

2 3
(0) X1 E
(0)
t
En t
(1) k
j n (t)i = N ( ) 4e i ~ j n i + Cnk (t) e i ~ j ki
5: (13.24)
k6=n
Using Eqs. (11.15) and (11.16), the eigenvalue equation for the unperturbed
system in Eq. (??) can be expressed as
2 3
X 1 (0)
d 4 i En(0) t (1)
E
k
t
i~ e ~ j ni + Cnk (t) e i ~ j k i5
dt
k6=n
2 3
(0) X1 E
(0)
t
En t
= H^0 + H ^ (1) (t) 4e i ~ j n i + (1) k
Cnk (t) e i ~ j k i5(13.25)
;
1
k6=n
keeping only the terms to …rst order in ; we may write

(0) 1
X E
(0)
t
En t
(1) (0) k
En(0) e i ~ j ni + Cnk (t) Ek e i ~ j ki
k6=n
1
X (1) (0)
dCnk (t) i
E
k
t
+i~ e ~ j ki
dt
k6=n
(0) (0) 1
X E
(0)
t
En t En t
^ 1 (t) e (1) (0) k
= En(0) e i ~ j ni + H i ~ j ni + Cnk (t) Ek e i ~ j ki ;
k6=n
(13.26)
or
1
X (1) (0) (0)
dCnk (t) i
E
k
t
i
En t
^ 1 (t) j
i~ e ~ j ki = e
~ H ni (13.27)
dt
k6=n
Now multiplying by h mj ; we have

1
X (1) (0) (0)
dCnk (t) i
E
k
t
i
En t
^ (t) j
i~ e ~ h m j ki =e ~ h m j H1 ni (13.28)
dt
k6=n
so that for m = k 6= n; we …nd

(1) (0) (0)
dCnm (t) i
Em t
i
En t
^ (t) j
i~ e ~ =e ~ h m j H1 ni (13.29)
dt
13.1. TIME DEPENDENT PERTURBATION THEORY 349
or
(1) (0) (0)
dCnm (t) 1 (Em En t)
^ (t) j
= ei ~ h m j H1 ni (13.30)
dt i~
which we may rewrite as an integral form
Zt
0
(1)
Cnm (t) = ei!mn t h ^ (t0 ) j
m j H1
0
n i dt ; (13.31)
0
where
(0) (0)
Em En
! mn = ; (13.32)
~
is known as transition frequency for the unperturbed system initially in the state
j n i make the transition to the state j m i after the interaction is turned on.
Thus
2
(1)
Pmn = Cnm (t)
is the probability for this transition to take place.
Example 13.1 A particle of charge q in a one-dimensional harmonic oscillator

of characteristic frequency ! is placed in an electric …eld that is turned on
and o¤ so that the potential energy is
^ 1 (t) = qE x t2 = 2
H ê :
If the particle is initially in the ground state, what is the probability that
after time t, such that t >> ; the particle is found in the …rst excited
state of the harmonic oscillator? What is the probability that it is found
in the second excited state?
Solution: We recall the ladder operators

r r
y m! p^ m! p^
a
^ = x
^ ip ;a
^= ^ + ip
x (13.33)
2~ 2m~! 2~ 2m~!
r
~
) x
^= a ^y
^+a (13.34)
2m!
so that r
^ 1 (t) = qE ~ t2 = 2
H a ^y e
^+a :
2m!
The particle is initially is in the ground state, which means
j ni = j0i
and the transition probability amplitude becomes

Zt r
(1) i! mn t0 t02 = 2 ~
C0m (t) = e e qE hmj a ^y j0i dt0
^+a
2m!
0
Zt r
i! mn t0 t02 = 2 ~
= e e qE hmj 1i dt0
2m!
0
r Zt
~ 02 2
i! mn t0 )
= qE e (t = 0
1m dt ; (13.35)
2m!
0
Homework: Complete the example... and read about Fermi-Golden rule

which I hope to cover it when we study about atom …eld interaction...
13.2 Electromagnetic waves in vacuum

We begin with a classical equations for EM waves in Vacuum. We recall from
Theo. Phys. III (sec. 7.7 ) that Maxwell’s equations in a medium with a free
~ are given by
charge density, ; and a free current density, J;
~ =
r E ~ = 0;
;r B
0
~ ~
r ~ + @ B = 0; r
E ~
B 0 0
@E
= ~:
0J (13.36)
@t @t
For a free space where there is no charge and current
= 0; J~ = 0 (13.37)
the Maxwell’s equations become

~ = 0; r E
r B ~ = 0;
~ ~
r E~ = @B ; r B ~ = 0 0
@E
: (13.38)
@t @t
Using the relation
r r ~ =r r A
A ~ ~
r2 A (13.39)
we may write
~ =r r E
~ ~ = @ ~
r r E r2 E r B (13.40)
@t
and using
~
@E
~ = 0; r
r E ~ =
B 0 0 (13.41)
@t
13.3. MONOCHROMATIC PLANE WAVES 351
we …nd !
~ 1 @2E~
~ = @
r2 E 0 0
@E ~ =
) r2 E (13.42)
@t @t c2 @t2
where
1
c= p =3 108 m=s (13.43)
0 0
is the speed of light in a vacuum. Fallowing a similar procedure we …nd for the
magnetic …eld
2~
~ = 1 @ B
r2 B (13.44)
c2 @t2
This means the electric and magnetic …elds satisfy the three dimensional wave
equation the solution of which is given by a three-dimensional wave function.
13.3 Monochromatic Plane waves

A monochromatic plane wave propagating along the z direction has the follow-
ing two properties:
(1) It is monochromatic: has a single frequency (or wave length)
(2) It is plane: For example if we consider an EM wave propagating along the

positive z-direction the oscillating electric and magnetic …elds are indepen-
dent of the x and y coordinates. In other words the …eld remain constant
on the x-y plane at a given instant of time. Plane electromagnetic …elds
can the be expressed as
~ (z; t) = E
E ~ 0 ei(kz !t) ~ (z; t) = B
;B ~ 0 ei(kz !t)
(13.45)
~ 0 and B
Note that here E ~ 0 represent are the complex electric and magnetic
…eld amplitudes.
Example 12.1 Show that the plane wave equations satisfy the Maxwell’s equa-
tions provided that
(a) The electric and magnetic …elds are transverse. This means for a wave
propagating along the z direction, E0z = B0z = 0:
(b) The electric and magnetic …elds are related by

h i
~ = E0 exp i ~k ~r !t +
E n
^;
h i
~ = E0 exp i ~k ~r !t +
B k^ n
^ ; (13.46)
c
where k^ and n^ are the unit vectors along the direction of propagation and
polarization, respectively.
Solution:
(a) Let’s consider whether the equations for the electric and magnetic …elds in-
deed satisfy Maxwell’s equation. We …rst begin by checking the divergence
~ and B
of E ~ for a plane monochromatic waves,
~ (z; t) = r ~ 0 ei(kz !t) @ @

r E E = E0x ei(kz !t) + E0y ei(kz !t)
@x @y
@ !t) @E0x @E0y @E0z
+ E0z ei(kz !t)
= ei(kz + + ikE0z +
@z @x @y @z
(13.47)
For plane waves propagating along the z-direction we know that the …elds
do not depend on x and y
@E0x @E0y
= = 0: (13.48)
@x @y
The waves are propagating in a vacuum (non absorptive medium) the
amplitude is constant
@E0z
=0 (13.49)
@z
Thus
~ (z; t) = ei(kz !t) ikE0z :
r E (13.50)
If this wave has to satisfy Maxwells equation, then
~ (z; t) = 0 ) E0z = 0:
r E (13.51)
This tells as the electric …eld is transverse. Which means it oscillates
on a plane normal to the direction of propagation. Following a similar
procedure we can show that
~ (z; t) = 0 ) B0z = 0:
r B (13.52)
(b) Now let’s apply Faraday’s Law for electric and magnetic …elds in a vacuum
~
@B
r ~ =
E : (13.53)
@t
Using what we already found, E0z = B0z = 0; we can write
2 3
x
^ y^ z^ B0x ei(kz !t)
@ @ @ @ 4 5
@x @y @z = B0y ei(kz !t)
i(kz !t) i(kz !t) @t
E0x e E0y e 0 0
@ @
) E0y ei(kz !t)
x
^+ E0x ei(kz !t)
y^
@z @z
@ @
+ E0y ei(kz !t)
E0x ei(kz !t)
z^
@x @y
= i!B0x ei(kz !t)
^ + i!B0y ei(kz
x !t)
y^ (13.54)
Recalling that for a plane wave E0x and E0y are constant, we …nd
ikE0y ei(kz !t)

^ + ikE0x ei(kz
x !t)
y^ = i!B0x ei(kz !t)
^ + i!B0y ei(kz !t) y^
x
(13.55)
There follows that
k k
kE0y = !B0x ; kE0x = !B0y ) B0x = E0y ; B0y = E0x (13.56)
! !
Noting that
~k = k^ ~ 0 = E0x x
z; E ~ 0 = B0x x
^ + E0y y^; B ^ + B0y y^ (13.57)
we can write
~ 0 = 1 ~k
B ~ 0 = k k^
E ~ 0:
E (13.58)
! !
Using the relations
2 2 c k 1
k= ;c = f ) ! = 2 f = ) = (13.59)
! c
we …nd
~ 0 = 1 k^ E
B ~ 0 ) B0 = 1 E0 (13.60)
c c
Generally the electromagnetic waves can propagate in any direction and
we can de…ne the wave vector ~k which has a magnitude equal to the wave
number
2
k= (13.61)
and its direction describes the direction of propagation of the wave. In

terms of the wave vector and the polarization direction we can then de-
scribe the electric and magnetic …elds for plane electromagnetic waves as
h i
E~ = E0 exp i ~k ~r !t + n
^;
h i
B~ = E0 exp i ~k ~r !t + k^ n^ : (13.62)
c
Note that the electric, magnetic, and the wave vector form an orthogonal
set of vectors
k^ n
^ = 0; k^ n^ n ^ = 0: (13.63)
13.3.1 The wave equation in terms of the potentials

Since the magnetic …eld can easily be determined from the electric …eld we will
consider the wave equation for the electric …eld
!
@ @ ~
E 2~
~ =
r2 E 0 0 ) r2 E ~ = 1 @ E: (13.64)
@t @t c2 @t2
We also recall that generally the electric and magnetic …elds are related to the
scalar and vector potential by
~
@A
~ (~r; t) =
E rV ~ (~r; t) = r
;B ~
A (13.65)
@t
In Theo Phys. III (Sec. 10.3) we were introduced to two types of Gauge
transformations (Lorentz and Coulomb gauges) as two di¤erent ways of solving
the wave equation by expressing in terms of the potentials of our choice. Gauge
transformations basically allows you to chose the vector potential. For the prove
of that you can refer to In Theo Phys. III (Sec. 10.3). In Coulomb Gauge we
choose a vector potential such that
~ = 0:
r A
The two Maxwell’s equations (Gauss’s law and Ampere/ Maxwells law)
~ = 0 ) r2 V + @ r A
r E ~ = 0 ) r2 V = @ r A ~ ;
@t @t !
~ ~
r B~ = 1 @E ) r r A~ = 1 @ rV
@A
2
c @t 2
c @t @t
!
~
)r r A ~ ~= 1 @
r2 A rV
@A
; (13.66)
c2 @t @t
Consider a vector potential de…ned by

Z t Z t
~ 0
A =A+ ~ ~=A
(rV ) dt0 ) A ~0 (rV ) dt0 (13.67)
0 0
then
Z t Z t
~0 = r A
r A ~+ ~+
r (rV ) dt0 = r A r2 V dt0
0 0
Z t
~ @ ~ dt0 = r A ~ r A ~=0
=r A 0
r A (13.68)
0 @t
)r A~ 0 = 0: (13.69)
where we used Gauss’s law

@ ~ :
r2 V = r A
@t
Noting that
Z t Z t
~ =r r
r r A ~0
A (rV ) dt0 ~0
=r r A r2 V dt0 ;
0 0
and applying the result

~0 = 0
r A
one …nds Z t
~ =
r r A r r2 V dt0 : (13.70)
0
Furthermore, we have
Z t Z t
~ = r2 A
r A2 ~0 r 2 ~0
(rV ) dt = r A0 2
r r2 V dt0 (13.71)
0 0
where we switched the order of the Laplacian and the gradient operators, and
! Z t
1 @ ~
@A 1 @ @ ~0 @
rV = rV A + (rV ) dt0
c2 @t @t c2 @t @t @t 0
!
1 @ @ ~0 1 @ @A~ 1 @2A ~0
= 2 rV A + rV ) 2 rV = (13.72)
c @t @t c @t @t c2 @t2
Then in terms of the new vector potential, Ampere/ Maxwells law,

!
1 @ @A~
r r A ~ 2~
r A= 2 rV (13.73)
c @t @t
becomes
Z t Z t ~0
2 2~0 + r 1 @2A
r r V dt 0
r A r2 V dt0 =
0 0 c2 @t2
1 @2A~0
) r2 A ~0 =0 (13.74)
c @t2
2
The electric …eld in terms of the new vector potential

~
@A
~ =
E rV (13.75)
@t
becomes
~0 Z t ~0
~ = @A @ @A
E rV (rV ) dt0 = rV + rV
@t @t 0 @t
@A~0
~ =
)E (13.76)
@t
Therefore for EM waves in free space with no charges and currents, in Coulomb
gauge, the …elds can be expressed as
@A~
~ (~r; t) =
E ~ (~r; t) = r A;
;B ~ (13.77)
@t
where the vector potential satis…es the wave equation
1 @2A~ (~r; t)
~ (~r; t)
r2 A = 0: (13.78)
c2 @t2
and we have dropped the prime for the sake of simplicity.
13.3.2 The vector potential for plane EM waves
Let’s consider plane x-polarized EM waves propagating along the z-direction

con…ned in a cube of length L. Inside this cube the vector potential is determined
by the wave equation in Eq. (13.78) and the solution to this equation can
be determined using separation of variables that we were introduced in Theo.
Phys. I sec 13.2 ). We recall that for a plane monochromatic EM waves polarized
Figure 13.1: Electromagnetic waves con…ned in cube of length, L.
along the direction described by the unit vector, n

^ ; the electric and magnetic
…elds are related by
h i
~ = E0 exp i
E ~k ~r !t + n
^;
h i
~ = E0 exp i
B ~k ~r !t + k^ n
^ ; (13.79)
c
where the electric, magnetic, and the wave vector form an orthogonal set of
vectors
k^ n
^ = 0; k^ n
^ n
^ = 0: (13.80)
For an x-polarized plane EM wave propagating along the z-direction one can
then write the …elds in terms of the vector potential as
@A~ (z; t) @Ax (z; t)

~ (z; t)
E = E (z; t) x
^= = x
^;
@t @t
x
^ y^ z^
~ (z; t) ~= @ @ @ @Ax (z; t)
B = r A @x @y @z = y^ (13.81)
@z
Ax (z; t) 0 0
and the equation for the vector potential
~ (~r; t)
1 @2A
~ (~r; t)
r2 A = 0; (13.82)
c2 @t2
becomes
@2 1 @ 2 Ax (z; t)
Ax (z; t) = 0: (13.83)
@z 2 c2 @t2
Using separation of variables
Ax (z; t) = Z (z) T (t) (13.84)
one …nds
d2 Z (z) Z (z) d2 T (t)
T (t) =0
dz 2 c2 dt2
2
1 d Z (z) 1 1 d2 T (t)
) = 0: (13.85)
Z (z) dz 2 c2 T (t) dt2
There follows that
1 d2 Z (z) 1 1 d2 T (t) ! 2kz

2
= kz2 ; 2 2
=
Z (z) dz c T (t) dt c2
d2 Z (z) d2 T (t)
) 2
+ kz2 Z (z) = 0; + ! 2kz T (t) = 0; (13.86)
dz dt2
where
! 2kz
kz2 =
:
c2
Noting that the solutions to Eq. (13.86) are given by
Z (z) = ckz eikz z + c kz e

ikz z
;
i! kz t i! kz t
T (t) = bkz e +b kz e
and the EM waves are con…ned within the volume

~ (z = 0; t)
E = ~ (z = L; t) = 0 ) Ax (z = 0; t) = Ax (z = L; t) = 0
E
) Z (z = 0) = Z (z = L) = 0:
one …nds
Z (z) = bkz sin (kz z) ; (13.87)
where
n
kz = kn = ; n = 0; 1; 2; 3:::
L
cn
! 2kz = c2 kz2 ) ! kz = ! n = (13.88)
L
and the solution to the wave equation
@2 1 @ 2 Ax (z; t)
Ax (z; t) = 0: (13.89)
@z 2 c2 @t2
can be written as
1
X
Ax (z; t) = bn ei!n t + b ne
i! n t
sin (kn z) (13.90)
n=0
Since the vector potential is a real quantity, we must have
Ax (z; t) = Ax (z; t)
i cn
L t i cn
L t i cn
L t i cn
L t
) bn e +b ne = bn e +b ne
bn = b n; b n = bn (13.91)
Therefore one can write the vector potential, the electric, and magnetic …elds
as
1
X
~ (z; t)
A = Ax (z; t) x
^= bn e i! n t
+ bn ei!n t sin (kn z) (13.92)
n=0
X1
~ (z; t) @Ax (z; t) i! n t
E = x
^= i! n bn e bn ei!n t sin (kn z) x
^(13.93)
;
@t n=0
X1
~ (z; t) @Ax (z; t) !n i! n t
B = y^ = bn e + bn ei!n t cos (kn z) y^ (13.94)
@z n=0
c
where
! n = ckn ; (13.95)
is the mode frequency and

n
kn = (13.96)
L
is the mode number. Introducing the complex variable
i! n t
ukn (t) = bn e ; ukn (t) = bn ei!n t
one can write

1
X
~ (z; t)
A = Ax (z; t) x
^= ukn (t) + ukn (t) sin (kn z) (13.97)
n=0
X1
~ (z; t) @Ax (z; t)
E = x
^= i! n ukn (t) ukn (t) sin (kn z) x
^;(13.98)
@t n=0
X1
~ (z; t) @Ax (z; t) !n
B = y^ = ukn (t) + ukn (t) cos (kn z) y^ (13.99)
@z n=0
c
13.3.3 Energy of the electromagnetic …eld

We recall the electromagnetic …eld energy is given by
Z
1 2 1 2
H = 0 jE (z; t)j + jB (z; t)j d
2 V 0
Z
L2 L 2 1 2
= 0 jE (z; t)j + jB (z; t)j dz: (13.100)
2 0 0
Noting that
2
jE (z; t)j = E (z; t) E (z; t)
1 X
X 1
= ! n ! m ukn (t) ukn (t) ukm (t) ukm (t) sin (kn z) sin (km z)
n=0 m=0
1 2 1
jB (z; t)j = B (z; t) B (z; t)
0 0
X1 X 1
!n !m
= ukn (t) + ukn (t) ukm (t) + ukm (t) cos (kn z) cos (km z)
n=0 m=0
c2
(13.101)
the energy becomes
1 1
L2 X X
H= 0 !n !m ukn (t) ukn (t) ukm (t) ukm (t)
2 n=0 m=0
Z L
!n !m
sin (kn z) sin (km z) dz + ukn (t) + ukn (t) ukm (t) + ukm (t)
0 c2
Z )
L
cos (kn z) cos (km z) dz (13.102)
0
and using the relations

Z L Z L
n m mn L
cos (kn z) cos (km z) dz = cos z cos z dz =
0 0 L L 2
Z L Z L
n m mn L
sin (kn z) sin (km z) dz = sin z sin z dz = (13.103)
0 0 L L 2
one …nds
1 1
L3 X X
H= !n !m 0 ukn (t) ukn (t) ukm (t) ukm (t)
4 n=0 m=0
1
+ ukn (t) + ukn (t) ukn (t) + ukn (t) mn
0c
1
X
0V
)H= ! 2n ukn (t) ukn (t) ukn (t) ukn (t)
4 n=0
1
X
0V
+ ukn (t) + ukn (t) ukn (t) + ukn (t) = ! 2n ukn (t) ukn (t) ;
2 n=0
(13.104)
where we used
V = L3 ; 0c
2
= 0:
We introduce position like, qkn (t) ; and momentum like, pks (t) ; canonical vari-
ables de…ned by
1 p i
ukn (t) = p mn qkn (t) + p pk (t) ;
0V ! n mn n
1 p i
ukn (t) = p mn qkn (t) p pk (t) ; (13.105)
0V ! n mn n
where mn is a constant with dimension of mass that we will set to one later.
Then the Hamiltonian in Eq. (13.104) can be expressed as
1 1
" #
0V
X 0V
X ! 2n p2kn (t)
2 2
H= ! uk (t) ukn (t) = mn qkn (t) + 2 ;
2 n=0 n n 2 n=0 0 V ! n mn
which we can be put in the form

1
" #
X 1 p2kn (t)
2 2
H= mn ! n qkn (t) + : (13.106)
n=0
2 2mn
One can easily recognize that the Hamiltonian represents the energy of a system
of independent harmonic oscillators. Then, more generally, the energy, the
vector potential, the electric …eld and the magnetic …eld can then be expressed
as
1 Xh 2 2 i
H= ! k qks (t) + p~2ks (t) ; (13.107)
2
~
k;s
X
~ t) = p1
A(r; q~ks (t) +
i ~
p~ks (t) ~~ks eik ~r + C:C ; (13.108)
2 0V !k
~
k;s
Xn o
~ t) = pi
E(r;
~
! k q~ks (t) + ip~ks (t) ~~ks eik ~r C:C ; (13.109)
2 0V ~
k;s
13.4. CANONICAL QUANTIZATION 361
X
~ t) = p1
B(r; q~ks (t) +
i
p~ (t) ~k
~
~~ks eik ~r C:C ; (13.110)
2 0V ~ ! k ks
k;s
where we set mn = 1 and considered a generalized complex the unit polarization

direction,~~ks ; here C:C means complex conjugate.
13.4 Canonical Quantization

In order to describe the EM …eld in quantum mechanics, we have to associate
Hilbert space operators with the dynamical variables, which do not all commute
in general. According to the postulates of quantum mechanics each pair of
canonically conjugate operators q^~ks and p^~ks has the none zero commutator i~.
This means
q^~ks ; p^~ks = q^~ks p^~ks p^~ks q^~ks = i~ (13.111)
More generally we may write
q^~ks ; p^~k0 s0 = q^~ks p^~k0 s0 p^~k0 s0 q^~ks = i~ ~

k~k0 ss
0
q^~ks0 q^~k0 s0 = 0; p^~ks0 p^~k0 s0 = 0: (13.112)
We recall the energy of the electromagnetic wave

1 Xh 2 2 i
H= ! k qks (t) + p~2ks (t) : (13.113)
2
~
k;s
Let’s make the classical energy of the EM waves be dimensionless. We can make
this by dividing Eq. (this by
Ek = ~! k : (13.114)
which we pretend that we do not know the energy of a photon. What we know
is it has dimension of energy Eq. (13.113). This leads to
X 1 1
H= p ! k qks (t) + ip~ks (t) p ! k qks (t) ip~ks (t) : (13.115)
~
2~! k 2~! k
k;s
If we introduce a complex variable a~ks

1
a~ks = p ! k qks (t) + ip~ks (t) (13.116)
2~! k
and its conjugate a~ks
1
a~ks = p ! k qks (t) ip~ks (t) (13.117)
2~! k
the classically dimensionless energy can be write as
1X
H= a~ks a~ks + a~ks a~ks : (13.118)
2
~
k;s
We note that we have included both a~ks a~ks and a~ks a~ks . This is critical in
quantum mechanics because these two ordering could lead to two di¤erent result
if the two operators corresponding to the two variables a~ks and a~ks do not
commute. In going from classical to quantum we replace the dynamical variables
q~ks and p~ks by operators q^~ks and p^~ks and the complex variable a~ks and a~ks by
an operator a ^~y (its adjoint operator). This leads to
^~ks and a
ks
1 1
^~ks = p
a ! k q^~ks + i^ ^~y = p
p~ks ; a ! k q^~y p~y
i^ : (13.119)
2~! k ks 2~! k ks ks
For any physical observables that you can measure experimentally the corre-
sponding operators must be really or in quantum mechanical term the operators
must be Hermitian and satisfy the condition
q^~ks = q^~y ; p^~ks = p^~y : (13.120)

ks ks
In terms of the operators in Eq. (13.119), we can then write the quantum
Hamiltonian as X
H^ =1 a ^~y + a
^~ks a ^~y a
^ks (13.121)
2 ks ks ~
~
k;s
Now let’s check whether a ^~ks and a^~y do commute or not. In terms of these
ks
operators, we may write
r r
~! k h y i ~! k h y i
q^~ks = a
^~ + a ^~ks ; p^~ks = i a
^~ a
^~ks ; (13.122)
2 ks 2 ks
so that using the commutation relation for the canonical operators
q^~ks ; p^~ks = q^~ks p^~ks p^~ks q^~ks = i~
we can show that the none Hermitian operator, a ^~y satisfy

^~ks and its adjoint a
ks
the following commutation relation
h i
a ^~y = 1:
^~ks ; a
ks
Then substituting
a ^~y = 1 + a
^~ks a ^~y a
^~ks (13.123)
ks ks
in the quantum Hamiltonian
X 1
^ =
H ^~y a
~! k a ^~ks + : (13.124)
ks 2
~
k;s
The contribution ~! ~
2 to the energy of each k; s oscillator mode is the so-called
zero point contribution. It is the re‡ection of the fact that, according to the un-
certainty principle, a quantum-mechanical harmonic oscillator can never come
13.5. STATE OF THE ELECTROMAGNETIC FIELD 363
to rest, not even in the ground state. In quantum optics this energy is called
vacuum mode energy.
The none Hermitian operator a ^~y are called photon
^~ks and its conjugate a
ks
annihilation and creation operators, respectively. Noting that the quantum
vector potential, electric …eld, and magnetic …eld operators from Eqs. (13.108-
13.110) can be expressed as
b~ 1 Xn ~
o
A(r; t) = p ! q^~ks (t) + i^
p~ks (t) ~~ks eik ~r + C:C ; (13.125)
2! 0V ~
k;s
Xn o
~ t) = pi
b
E(r; ! q^~ks (t) + i^
p~ks (t)
~
~~ks eik ~r C:C ; (13.126)
2 0V ~
k;s
b i Xn ~
o
~ t) =
B(r; p p~ks (t) ~k
! q^~ks (t) + i^ ~~ks eik ~r C:C ; (13.127)
2! 0V ~
k;s
in terms of the photon annihilation and creation operators, which we may write
as
p
2~!^
a~ks (t) = ! q^~ks (t) + i^p~ks (t) ;
r
2~ y i
a
^ (t) = q^~ks (t) p^~ (t) ; (13.128)
! ~ks ! ks
becomes
r
b~ ~ Xn ~ i~
o
A(r; t) = a ^~y (t)~~ks e
^~ks (t)~~ks eik ~r + a k~r
(13.129)
2 0 !V ks
~
k;s
r
b ~! X n ~ i~
o
~ t) = i
E(r; a^~ks (t)~~ks eik ~r ^~y (t)~~ks e
a k~r
(13.130)
2 0V ks
~
k;s
r
b ~ Xn ~ i~
o
~ t) = i
B(r; a^~ks (t) ~k ~~ks eik ~r ^~y (t) ~k
a ~~ks e k~r
(13.131)
2 0 !V ks
~
k;s
The results in Eq. (13.129)-(13.131) are foundations upon which quantum optics
is built on.
13.5 State of the electromagnetic …eld

In the study of the quantum states of the electromagnetic wave we shall consider
a single linearly polarized mode. For a single linearly polarized mode we recall
that
~~ks = ~~ks = ~; a
^~ks (t) = a
^ (t)
and the quantized electric …eld in Eq. (13.130) becomes

h i
b
~ t) = il (!)~ a ~ ~
E(r; ^y (t) e ik ~r a
^ (t) eik ~r ; (13.132)
where r
~!
l (!) = : (13.133)
2 0V
Using
i!t
a
^ (t) = a
ê ^y (t) = a
)a ^y ei!t (13.134)
the electric …eld operator can be put in the form
h i
b ~ ~
~ t) = il (!)~ a
E(r; ^y e i(k ~r !t) a êi(k ~r !t)
n h i o
= il (!)~ a ^y a^ cos ~k ~r !t ^ sin ~k ~r !t
^y + a
i a
nh h ii h i
b
~ t) = l (!)~ i a
) E(r; ^y a ^ cos ~k ~r !t + a ^y + a^ sin ~k ~r !t
(13.135)
Introducing two dimensionless Hermitian operators de…ned by
a ^y + a
^1 = a ^; a ^y
^2 = i a a
^ (13.136)
with the commutation relation
[^
a1 ; a ^y + a
^2 ] = a ^y
^; i a a
^
y y y
) [^
a1 ; a
^2 ] = i a
^ ;a
^ a
^ ;a
^ + a ^y
^; a [^
a; a
^]g
y y
) [^
a1 ; a
^2 ] = i a
^ ;a
^ + a
^; a
^ ) [^
a1 ; a
^2 ] = i a ^y + a
^; a ^y
^; a
) [^
a1 ; a
^2 ] = 2i (13.137)
we can rewrite the electric …eld operator as

n o
b
~ t) = l (!)~ a
E(r; ^1 sin ~k ~r !t + a ^2 cos ~k ~r !t : (13.138)
We note that a
^1 and a
^2 behave like dimensionless canonical conjugates with the
commutation relation
[^
a1 ; a
^2 ] = 2i: (13.139)
Thus recalling that the uncertainty relation for two canonical conjugate opera-
tors C^ and D
^ is given by
2 2 1 Dh ^ ^ iE 2
C^ ^
D C; D (13.140)
4
we may write for the two dimensionless canonical conjugate variable, the uncer-
tainty relation rD ErD E
2 2
( a
^1 ) ( a^2 ) 1
13.5. STATE OF THE ELECTROMAGNETIC FIELD 365
From the expression for the electric …eld operator we note that a ^1 and a
^2 are
also the amplitudes of the quadratures into which the oscillating …eld can be
decomposed. Because of D this a ^1E and a
^D2 are called
E …eld quadrature operators.
2 2
Based on the values of ( a ^1 ) and ( a ^2 ) the sate of the EM radiation
are classi…ed as:
Coherent State: D E D E
2 2
( a ^1 ) = ( a ^2 ) = 1
N.B.: This is also true for a vacuum mode

Thermal State: D E D E
2 2
( a^1 ) > 1; ( a
^2 ) > 1
Squeezed State: D E D E
2 2
( a
^1 ) < 1; ( a
^2 ) > 1
Squeezed state of light is purely quantum mechanical property of the EM

2
wave. There is no way that classical theory of EM wave can account for ( a
^1 ) <
1: Theory of squeezing of the electromagnetic waves show up in numerous sit-
uations in which EM waves interact with a nonlinear medium. Examples are
resonance ‡uorescence, harmonic generation, four wave mixing, parametric am-
pli…cation, parametric down conversion, and optical bistability. Experimentally,
squeezing was observed for the …rst time in 1985 in the process of fourwave
mixing. Much larger squeezing have been observed in the process of parametric
down-conversion. One area of application of squeezed light is in the gravita-
tional waves detection. Gravitational waves were predicted by Albert Einstein
as a consequence of his general theory of relativity have recently been directly
measured using, which I suspect, squeezed EM waves.
Chapter 14
Quantum description of
charge-…eld interaction
14.1 Classical to quantum approach

It always important to begin with simple classical description of any interaction
before we get into the quantum description. When we deal with the interaction
of an EM waves with a charged particle with charge e (like the electron), we need
to think what do the …elds of the electromagnetic wave do the charged particle.
It simple, it just create a force that changes the momentum of the particle.
Here we are interested in con…ned charged particles like the electrons in an
atom. The electrons are in a central force …eld described by a potential U (~r)
due to of which the electrons posses a momentum p~c (t) that can be determined
from the central force F~C by
Z
d~
pc (t)
= Fc ) p~c (t) = F~c dt:
~ (14.1)
dt
When the atom is exposed to an electromagnetic waves, it experiences an addi-
tional force, F~I that results in an additional momentum p~I (t)
Z
d~
pI (t)
= F~I ) p~I (t) = F~I dt: (14.2)
dt
This interaction force, though it in involves both electrical and magnetic, it can
be determined from the electrical …eld only as we have already seen the magnetic
…eld is related to the electric …eld by the speed of light for plane electromagnetic
waves. Thus we may this force on a particle with charge e as
~
@A
F~I = eE
~ = e (14.3)
@t
where we have used
~
@A
~ =
E (14.4)
@t
367
368CHAPTER 14. QUANTUM DESCRIPTION OF CHARGE-FIELD INTERACTION
in the column gauge. Then the momentum change due to the interaction can
be expressed as
Z ~
@A ~ (~r; t) :
p~I (t) = e dt = eA (14.5)
@t
The net momentum, p~ (t), of charged particle in a central force …eld like that of
the electron in a hydrogen atom should be written as
p~ (t) = p~c (t) + p~I (t) = p~c (t) ~ (~r; t) :

eA (14.6)
Now let’s consider a charged particle, e, in a central force …eld is located at a

position ~r0 and a plane electromagnetic wave which we describe by the vector
potential A~ (~r; t) : Then the total energy of the charged particle interacting with
this EM wave can be determined
p2 1 ~ (~r; t) ~ (~r; t) + eU (~r) (14.7)
HEF = + eU (~r) = p~c eA p~c eA
2m 2m
p2c e 2
~ (~r; t) p~c (t) + e A2 (~r; t)
~ (~r; t) + A
HEF = + eU (~r) p~c (t) A
2m 2m 2m
(14.8)
or
HEF = H0E + HI (14.9)
where
p2c
H0E = + eU (~r) (14.10)
2m
is the free energy of the charged particle in the absence of the EM waves and
2
e ~ (~r; t) p~c (t) + e A2
~ (~r; t) + A
HI = p~c (t) A (14.11)
2m 2m
is the interaction energy.
We make a transition from classical to quantum using the transformation
~r ! b
~r
p~c (t) ! p~bc (t) ! i~r
r
b~ ~ Xn ~
o
i~
~
A (~r; t) ! A (~r; t) = a ^~y (t)~~ks e
^~ks (t)~~ks eik ~r + a k~r
2 0 !L3 ks
~
k;s
so that the quantum Hamiltonian becomes
^ 0E = ~2 2
H r + eU (~r) (14.12)
2m
and
Î = ie~ b~ b~ e2 b 2
H r A (~r; t) + A (~r; t) r + A (~r; t) (14.13)
2m 2m
14.2. THE DIPOLE APPROXIMATION 369
and of course we have the free energy of the EM …eld

Z X
1 1 ^2 1
^ F
H0 = ^2
0E + B d = ^~y a
~! k a ^ks + : (14.14)
2 ks ~ 2
0 ~
k;s
We will focus on the …eld-atom interaction part of the Hamiltonian. To this

end, we note that our goal eventually to solve the Schrödinger equation
@ (~r; t) ^
i~ =H (~r; t) : (14.15)
@t
This means the interaction part of the Hamiltonian acts on the wave function.
Taking this into consideration we note that
b~ b~ b~
r A (~r; t) (~r; t) =A (~r; t) r (~r; t) + (~r; t) r A (~r; t) (14.16)
but recalling that in the Coulumb gauge

b~
r A (~r; t) = 0 (14.17)
we …nd
b~ b~
r A (~r; t) (~r; t) =A (~r; t) r (~r; t) : (14.18)
This means the interaction Hamiltonian in Eq. (14.13) can be expressed as
Î = ie~ b~ e2 b 2
H A (~r; t) r + A (~r; t) (14.19)
m 2m
14.2 The dipole Approximation

It is very common in the study of atom-…eld interaction to apply the so called
dipole approximation. It is important to know what this approximation mean
and under what approximation it can be applied which we will discuss next.
Consider an atom located at the position described by ~r0 : The charged particle
bound to the nucleus of this atom is described by a position vector ~r: This atom
is immersed in an electromagnetic wave described by the vector potential A. ~
This vector potential at the position of the electron depends on the position
vector R~ = ~r0 + ~r as shown in the …gure below. Thus the exact interaction
Hamiltonian should be written as
Î = ie~ b~ e2 b 2
H A (~r0 + ~r; t) r + A (~r0 + ~r; t) (14.20)
m 2m
For the moment if we switch to a classical thinking, we may write the vector
potential
h i
~ (t) e~k (~r0 +~r) = A
~ (~r0 + ~r; t) = A
A ~ (t) e~k ~r0 e~k ~r = A
~ (t) e~k ~r0 1 + i~k ~r + :::
In the dipole approximation, we set

~k ~r ' 0 (14.21)
Physically this is applicable when the wavelength of the …eld is much bigger
than the size of the atom ( >> a0 ),
~k ~r 2 a0
ka0 = a0 '0 (14.22)
where a0 10 10 m is the Bohr radius. Therefore in the dipole approximation

the interaction Hamiltonian becomes
Î = ie~ b~ e2 b 2
H A (~r0 ; t) r + A (~r0 ; t) (14.23)
m 2m
To see why it is called a dipole approximation we express the wave function in

terms of the dipole approximated vector potential as
ie ~
(~r; t) = exp A (~r0 ; t) ~r (~r; t)
~
so that the Schoudinger equation
@ (~r; t) ^
i~ =H (~r; t) : (14.24)
@t
just for the interaction Hamiltonian (interaction picture) becomes
@ ie ~
i~ exp A (~r0 ; t) ~r (~r; t)
@t ~
ie~ b~ e2 b 2 ie ~
= A (~r0 ; t) r + A (~r0 ; t) exp A (~r0 ; t) ~r (~r; t) : (14.25)
m 2m ~
ie ~ @ ie @ ~
) i~ exp A (~r0 ; t) ~r [ (~r; t)] + (~r; t) ~r A (~r0 ; t)
~ @t ~ @t
ie ~ ie~ ~ (~r0 ; t) r ie A ~ (~r0 ; t) ~r e2 ~ (~r0 ; t)2 :
= exp A (~r0 ; t) ~r (~r; t) A + (~r; t) A
~ m ~ 2m
(14.26)
@ ie @ ~
) i~ [ (~r; t)] + (~r; t) ~r A (~r0 ; t) (14.27)
@t ~ @t
ie~ ~ (~r0 ; t) r ie A ~ (~r0 ; t) ~r e2 2
= (~r; t) A + (~r; t) A (~r0 ; t) :
m ~ 2m
(14.28)
14.2. THE DIPOLE APPROXIMATION 371
Noting that
ie ~ ie ~ (~r0 ; t) ~r
r A (~r0 ; t) ~r = r A
~ ~
ie n ~ ~ (~r0 ; t) + A
~ (~r0 ; t) ~ (~r0 ; t)
o
= A (~r0 ; t) r ~r + (~r r) A (r ~r) + ~r r A
~
and in the dipole approximation
r ~ (~r0 ; t) = 0; (~r r) A
A ~ (~r0 ; t) = 0
also ~r is irrotational vector

r ~r = 0
we …nd
ie ~ ie ~ ie ~
r A (~r0 ; t) ~r = A (~r0 ; t) r ~r = A (~r0 ; t)
~ ~ ~
so that
@ ie @ ~
i~ [ (~r; t)] + (~r; t) ~r A (~r0 ; t)
@t ~ @t
2
ie~ ~ (~r0 ; t) ie A ~ (~r0 ; t) + e 2
= (~r; t) A (~r; t) A (~r0 ; t) : (14.29)
m ~ 2m
@ ie @ ~ 3e2
i~ [ (~r; t)] + (~r; t) ~r A (~r0 ; t) = (~r; t) A2 (~r0 ; t) : (14.30)
@t ~ @t m
In the Coulomb gauge we can replace
~ (~r0 ; t) = @ ~
E A (~r0 ; t)
@t
so that
@ ~ (~r0 ; t) 3e2
i~ [ (~r; t)] e~r E (~r; t) = (~r; t) A2 (~r0 ; t) : (14.31)
@t 2m
or
@ ^ I (~r; t) :
i~ (~r; t) = H (14.32)
@t
where
2
^ I = e~r E
H ~ (~r0 ; t) + 3e A^2 (~r0 ; t) :
b
2m
The second terms in the above expression is negligible compared to the …rst term
especially for low intensity …elds. Suppose the atom is at the origin(~r0 = 0), we
may write the electric …eld as
b
~
b ~ 0 cos (!t) ) A^ (~r0 ; t) = E 0 sin (!t)
b
~ (~r0 ; t) = E
E
!
for the position of the electron assuming resonance condition we may write
~r = ~a0 cos (!t) :
For the average interaction energy we can write

D E 2
^ I = ea0 E0 cos2 (!t) + 3e E02 sin2 (!t) :
H
2m! 2
we note that
19 2 6 2
e2 e2 2 10 10 10 50
35
! = = 10 (14.33)
m! 2 mc2 10 31 (108 )2 10 15
19 10 29
ea0 10 10 = 10
Also for few photons interacting with an atom we really need to have low inten-
sity …eld. As result of this and the two order of magnitude we compared above
the second term is usually negligible compared to the …rst term. Consequently
the interaction Hamiltonian can be approximated as
b
^ I ' e~r E b
~ (~r0 ; t) = p~ E
~ (~r0 ; t) :
H (14.34)
where
p~ = e~r (14.35)
is the dipole moment of the bound charges with charge magnitude e. This is
why it is called the dipole approximation.
14.3 Atom-…eld interaction Hamiltonian

The interaction of the radiation …eld with a Hydrogenlike atom (single electron
atom) in the dipole approximation can be described by the Hamiltonian
^ =H
^F + H
Â b
~ (~r0 ; t) ;
H e~r E (14.36)
where H ^ A and H^ F are the Hamiltonian for the atom and the …eld in the absence
of interaction. We already know that the Hamiltonian for …eld in the absence
of interaction is given by
X 1
^ =
H ^~y a
~! k a ^~ks + : (14.37)
ks 2
~
k;s
For the free atom Hamiltonian we recall from our study of Hydrogenlike atoms
energies takes discrete values which we described by
Z 2 ( 13:6ev)
En = (14.38)
n2
14.3. ATOM-FIELD INTERACTION HAMILTONIAN 373
where n takes positive integral values. We will express this energy in terms of
atom transition operators de…ned as
^ nm = jni hmj : (14.39)
These operator have similar property to the projection operators that we intro-
duced in Quantum I. Suppose the atom is in the state jmi ; then
^ nm jmi = jni hmj mi = jni : (14.40)
This means the action of the transition operator has caused the atom to make
a transition from jmi to jni : We also recall that the atomic eigen state form a
complete set, X
jni hnj = 1: (14.41)
n
Thus using this completeness relation we may write the Hamiltonian for the
atom as X X
HÂ = En jni hnj = En ^ nn (14.42)
n n
In the interaction part of the Hamiltonian, similarly, using the completeness

relation we may write the dipole moment of the atom as
X X X X X
e~r = jmi hmj e~r jni hnj = jmi hmj e~r jni hnj = mn jmi hnj = mn ^ mn
m n m;n m;n m;n
where
mn = hmj e~r jni
is the electric-dipole transition matrix element. Recalling that the electric …eld,
b~ (~r0 ; t), in the dipole approximation, is evaluated at the position of the atom
E
and using the quantized electric …eld operator we derived in the previous section
r
b
~ ~! X n i~
k~r0 y i~
k~r0
o
E(r; t) = i a
^~ ~~ e a
^ ~ e ; (14.43)
2 0 L3 ks ks ~ks ~ks
~
k;s
The interaction Hamiltonian can be then be written as

r
b X ~! X n ~ i~
o
^ ~
HI = e~r E (~r0 ; t) = mn ^ mn i 3
^~ks~~ks eik ~r0
a ^~y ~~ks e
a k~r0
;
m;n
2 0 L ks
~
k;s
(r (14.44) )
r
XX ~! ~!
Î = i~
k~r0 i~
k~r0 y
)H ^ mn i mn ~~ks e a
^~ks i mn ~~ks e a
^~ ;
m;n ~
2 0 L3 2 0 L3 ks
k;s
(14.45)
or XXn o
Î = ~
)H mn
g~ks ^ mn a ^~y ;
^~ks + g~ksmn ^ mn a (14.46)
ks
m;n ~
k;s
where r
mn ~! mn ~~ks ~
g~ks = eik ~r0 : (14.47)
2 0 L3 ~
Then the quantum Hamiltonian that describes the interaction of a Hydrogenlike
atom with the radiation …eld in the dipole approximation is given by
X 1 X XXn o
H^ = ~! k a^~y a^~ks + + En ^ nn +~ mn
i^ mn g~ks a ^~y
^~ks g~ksmn a ;
ks 2 n m;n
ks
~
k;s ~
k;s
(14.48)
mn
where g~ks given by Eq. (14.47) is known as atom …eld coupling constant. It
describes the strength of the dipole interaction between the atom and the …eld
of the radiation.
14.4 A single two-level atom and single mode

…eld interaction
As we have seen in our study of the hydrogen atom or the helium atom, the
energy of the electron consist of in…nite number of levels. However, in the
interaction of these or any other atom with the EM …eld, it can be made that
only to levels can be optically active while the remaining levels are optically
dark. This mean the electron can only make transition by absorbing or emitting
a photon between the two levels. In such cases the atom can be modeled as an
atom with only two energy levels as shown in the …gure. Suppose the ground
state is labeled as 1 and the excited state by 2 and the atom is located at the
origin (~r0 = 0). For a linearly polarized radiation …led (i.e. ~~ks = ~~ks ;is real),
we have
mn
g~ks = g~ksmn
since the atom is located at the origin. Then the Hamiltonian in Eq. (14.48)
X 1
^ =
H ^~y a
~! k a ^~k + + E1 ^ 11 + E2 ^ 22 (14.49)
k 2
~
k
Xn
+ i~ g~k11 ^ 11 a
^~k ^~y + g~k12 ^ 12 a
a ^~k ^~y
a (14.50)
k k
~
k
o
+g~k21 ^ 21 a
^~k ^~y + g~k22 ^ 22 a
a ^~k ^~y
a : (14.51)
k k
For a two-level atom the dipole transition matrix can be written as

h1j e~r j1i h1j e~r j2i 11 12
= =
h2j e~r j1i h2j e~r j2i 21 22
In the dipole interaction the electron absorbs a photons and make the transition
from the j1i to j2i or emits photon by making the transition from j1i to j2i.
This mean
e~r j1i = c j2i ; e~r j2i = d j1i
14.4. A SINGLE TWO-LEVEL ATOM AND SINGLE MODE FIELD INTERACTION375
Thus we have 12 = 21 and 11= 22 = 0 which leads to

r
~! 12 ~~
g~k12 = g~k21 = k
= g~k (14.52)
2 0 L3 ~
g~k11 = g~k22 = 0 (14.53)
so that
X 1 X
^ =
H ^~y a
~! k a ^~k + + E1 ^ 11 + E2 ^ 22 + ~ ig~k (^ 12 + ^ 21 ) a
^~k ^~y :
a
k 2 k
~
k ~
k
(14.54)
where r
~! 12 ~~k
g~k =
2 0 L3 ~
Introducing the atomic transition frequency de…ned by
~! = E2 E1
and using the completeness relation for two-level atom

2
X
jni hnj = j1i h1j + j2i h2j = ^ 11 + ^ 22
n=1
we may write
1 1
E1 ^ 11 + E2 ^ 22 = ~! (^ 11 ^ 22 ) + (E1 + E2 )
2 2
(Homework Assignment 1: show that above equation.) so that the Hamiltonian
can be written as
X 1 1 1 X
^ =
H ^~y a
~! k a ^~k + + ~! (^ 11 ^ 22 )+ (E1 + E2 )+~ ig~k (^ 12 + ^ 21 ) a
^~k ^~y :
a
k 2 2 2 k
~
k ~
k
(14.55)
We ignore the constant energy terms in the above expression since it has no
e¤ect in studying the quantum properties of the atom-…eld system. Thus the
Quantum Hamiltonian can be written as
X 1 X
^ =
H ^~y a
~! k a ^k + ~! (^ 11 ^ 22 ) + ~g~k (^ 12 + ^ 21 ) a ^~y : (14.56)
^~k + a
k ~ 2 k
~
k ~
k
where we have absorbed the imaginary i into the photon creation and annihila-
tion operators.
Homework Assignment 2: Show that the commutation relation
[^ kl ; ^ mn ] = ^ kn lm ^ ml kn (14.57)
Next we proceed to express the atom in terms of atom raising (^ + ) ; lowering

(^ ) ; and atomic conversion (^ z ) operators de…ned by
^ + = j2i h1j ; ^ = j1i h2j ; ^ z = ^ 11 ^ 22 : (14.58)
The quantum Hamiltonian becomes

X 1 X
^ =
H ^~y a
~! k a ^k + ~!^ z + ~g~k (^ + + ^ ) a ^~y :
^~k + a (14.59)
k ~ 2 k
~
k ~
k
From the commutation relation in Eq. (14.57)follows that the operators ^ + ;

^ ; and ^ z satisfy the spin-1/2 algebra of the Pauli matrices
[^ ; ^ + ] = ^z ;
[^ ; ^ z ] = 2^ ;
and in matrix notation these operators are given by
0 0 0 1 1 1
^ = ; ^+ = ; ^+ = :
1 0 0 0 0 1
The ^ operators takes an atom in the upper state into the lower state whereas
^ + takes an atom in the lower state into the upper state.
In most quantum studies of two-level atom interaction with the radiation
…eld, in addition to the dipole approximation, it is often common to use the
rotating wave approximation. Next we will determine the quantum Hamiltonian
in the rotating wave approximation. To this end, using
^ + = ^ + (0) ei!t ; ^ + = ^ (0) e i!t
a
^~k = a
^~k (0) e i! k t
^~y = a
;a ^~y (0) ei!k t
k k
we may write the equation
(^ + + ^ ) a ^~y = ^ + a
^~k + a ^~y ^ + ^ a
^~k + a ^~y ^ +
^~k + a
k k k
as
(^ + + ^ ) a ^~y = ^ + (0) a
^~k + a ^~k (0) ei(! ! k )t
^~y (0) ^ (0) e
+a i(! ! k )t
k k
+ ^ (0) a
^~k (0) e i(!+! k )t
^~y (0) ^ (0) ei(!+!k )t
+a
k
For near resonance interaction where the atomic transition frequency is close
to the photon frequency (! ' ! k ) the last two terms in the above expression
are a very rapidly changing function which add up approximately to zero. Thus
the last two terms are approximated to be zero under the rotating wave approx-
imation and we may write
(^ + + ^ ) a ^~y ' ^ + a
^~k + a ^~y ^ :
^~k + a
k k
14.4. A SINGLE TWO-LEVEL ATOM AND SINGLE MODE FIELD INTERACTION377
Then the quantum Hamiltonian becomes

X 1 X
^ =
H ^~y a
~! k a ^~k + ~!^ z + ~g~k ^ + a ^~y ^
^~k + a : (14.60)
k 2 k
~
k ~
k
This is the quantum Hamiltonian for a two-level atom interacting with the
radiation …eld in the dipole and rotating wave approximation.
Probability Amplitude method : In this approach we express the state vector

as time dependent amplitudes for each optically active state of the atom
j (t)i = cg (t) jGi + ce (t) jEi
so that the Shroudinger equation

@ h i
i~ j (t)i = H ^f + H
^ 0e + H ^ I j (t)i : (14.61)
0
@t
leads to
@ i h^ i
^ I (cg (t) jGi + ce (t) jEi) ;
(cg (t) jGi + ce (t) jEi) = H0 + H (14.62)
@t ~
@cg (t) @ce (t) i h^ i h
^ I cg (t) jGi + i H ^0 + H
i
^ I ce (t) jEi :
jGi + jEi = H0 + H
@t @t ~ ~
(14.63)
We note that since the atomic states that are optically active are only jGi and
jEi ; these states form a complete set. That means
jGi hGj + jEi hEj = 1:
Using this completeness relation we may write the quantum Hamiltonian for
the charged particle
^ e = (jGi hGj + jEi hEj) H
H ^ e (jGi hGj + jEi hEj)
0 0
^ 0e + jEi hEj H
= jGi hGj H ^ 0e (jGi hGj + jEi hEj)
^ 0e jGi hGj + jEi hEj H
= jGi hGj H ^ 0e jGi hGj + jGi hGj H
^ 0e jEi hEj + jEi hEj H
^ 0e jEi hEj
(14.64)
^ e = (jGi hGj + jEi hEj) H

H ^ e (jGi hGj + jEi hEj)
0 0
^ 0e + jEi hEj H
= jGi hGj H ^ 0e (jGi hGj + jEi hEj)
^ 0e jGi hGj + jEi hEj H
= jGi hGj H ^ 0e jGi hGj + jGi hGj H
^ 0e jEi hEj + jEi hEj H
^ 0e jEi hEj
(14.65)
Now if we use
^ e jGi = ~! g H
H ^ e jGi ; H
^ e jEi = ~! e jEi (14.66)
0 0 0
along with the orthonormality condition for the atomic eigenstates
hGj Gi = hEj Ei = 1; hGj Ei = hEj Gi = 0 (14.67)
we …nd
^ 0e = ~! g jGi hGj + ~! e jEi hEj :
H (14.68)
For a single mode EM wave the free Hamiltonian can be expressed as
^ f = ~! f 1
H0 ^y a
a ^+ :
2
In the dipole approximation the interaction Hamiltonian for an electron, from

Eq. (14.34), using the completeness relation for the atomic states as
Î = b
~ (~r0 ; t) = b
~ (~r0 ; t) :
H e~r E (jGi hGj + jEi hEj) e~r (jGi hGj + jEi hEj) E
(14.69)
Î =
H fjGi hGj e~r jGi hGj + jEi hEj e~r jGi hGj + jGi hGj e~r jEi hEj + jEi hEj e~r jEi hEjg
b
~ (~r0 ; t) :
E (14.70)
In the dipole interaction the electron absorbs a photons and make the transition
from the jGi to jEi or emits photon by making the transition from jEi to jGi.
Thus only the o¤ diagonal terms for the dipole moment matrix survives
Î = b
~ (~r0 ; t) ;
H eg jEi hGj + eg jGi hEj E (14.71)
where
eg = eg = hEj e~r jGi :
Using the the quantization for a single mode EM wave in the dipole approxi-
mation h i
b
~ t) = il (!)~ a ~ ~
E(r; ^y (t) e ik ~r0 a
^ (t) eik ~r0 ; (14.72)
Chapter 15
Scattering
15.1 Expression of the Cross section

15.2 The Born Approximation
15.3 An example of the Born approximation:
The Yukawa Potential
15.4 The method of Partial waves
379
380 CHAPTER 15. SCATTERING
Chapter 16
Introduction to relativistic
quantum mechanics
16.1 The Notations-Einstein’s notation

Lorentz transformation: If we want to describe an event that occurred some-
where on this planet, we must be able to tell exactly where (space) it occurred
and when (time). This means we must be able to tell the time at which the
event occurred and the exact position of this event in this space (three dimen-
sional space) as measured from some origin, O; on some reference frame S or
from another origin on another reference frame S 0 : The reference frame S 0 could
be in motion relative to S in an arbitrary manner. These reference frames could
be our home, our car that we are driving, a spacecraft traveling in the deep
outer space, or the international space station orbiting our planet. Suppose an
event in space described by the coordinates (x; y; z) is recorded at time t by
an observer at O on reference frame S, as shown in Fig. 16.1. Using "four
dimensional space", we may express this event as (t; x; y; z). Let’s say this same
event for an observer O0 on reference frame S is recorded at a di¤erent time t0
at a di¤erent point in space (t0 ; x0 ; y 0 ; z 0 ).The Lorentz transformation is de…ned
by
ct0 = (ct x) ; x0 = (x c t) ; y 0 = y; z 0 = z:
where
1 v
=q ; = : (16.1)
1 v2 c
c2
or using Matrices
2 3 2 32 3
ct0 0 0 ct
6 x0 7 6 0 0 7 6 x 7
6 0 7=6 76 7 (16.2)
4 y 5 4 0 0 1 0 54 y 5
z0 0 0 0 1 z
381
382CHAPTER 16. INTRODUCTION TO RELATIVISTIC QUANTUM MECHANICS
Figure 16.1: Two inertial reference frames. Inertial frame S 0 is moving with a
constant velocity along the poesitive x relative to inertial frame S.
or 2 3 2 32 3
ct0 cosh ( ) sinh ( ) 0 0 ct
6 x0 7 6 sinh ( ) cosh ( ) 0 0 7 6 x 7
6 0 7=6 76 7: (16.3)
4 y 5 4 0 0 1 0 54 y 5
z0 0 0 0 1 z
where
1
= tanh ( ): (16.4)
The Minkowski spacetime: 4-dimensional manifold that consist of space

and time. The time cordinate ct is represented by x0 and the space coordi-
nates (x; y; z) are represented by xj ; where j = 1; 2; 3. We use latin indices,
i; j; k; l::: to denote space coordinates. The combined space-time coordinates
are represented by Greekindices ; ; ; ::::. runing from = 0; 1; 2; 3: Therefore
in Minkowski spacetime, a point is described by x with = 0; 1; 2; 3 meaning
x0 ; x1 ; x2 ; x3 = (ct; x; y; z) = ct; xi
The interval: the interval de…ned by
2 2 2 2 2
( s) = x0 x1 x2 x3 (16.5)
in the Minkowski spacetime is invariant under the boost.

The worldline: Consider two events (Event 1 and Event 2 ). The line
joining these two events in the Minkowski spacetime is known as the worldline.
It could be a straight or wiggly line. If these two events are separated by an
in…nitesimally interval, ds; and the two events are described by (t; x; y; z) and
(t + dt; x + dx; y + dy; z + dz), we can write
ds2 = c2 dt2 dx2 dy 2 dz 2 : (16.6)

16.1. THE NOTATIONS-EINSTEIN’S NOTATION 383
The basis vectors: we can de…ne at every point P in the Minkowski space-
time a set of 4 coordinate basis vectors
~s
e^ = lim ; (16.7)
x !0 x
where ~s is the in…nitessimal separation vector between point P and some nearby
point Q with coordinate separation xa from P . For exampleThus eâ is the
Figure 16.2: The basis vectors.
tangent vector to the xa coordinate curve at the point P:

Covariant and controvariant components: Any vector …eld at point P;
~v (x ) ; in the Minkowski spacetime can be expressed as linear combination of
the basis vectors
~v (x ) = v 0 (x ) e^0 + v 1 (x ) e^1 + v 2 (x ) e^2 + v 3 (x ) e^3 ; (16.8)
where v are known as the controvariant components of the vector …eld, ~v (x ) ;

in the basis eâ : For any set of basis vectors we can de…ne another set of basis
vectors known as the dual basis vectors, e^ (x) ; de…ned by
1 =
e^ (x) e^ (x) = = : (16.9)
0 6=
The dual basis vectors, e^ ; and the basis vectors, e^ ; form a reciprocal system
of vectors. The vector …eld ~v (x) can also be expressed in terms of the dual basis
vectors as
~v (x ) = v0 (x ) e^0 + v1 (x ) e^1 + v2 (x ) e^2 + v3 (x ) e^3 ; (16.10)

where v are known as the covariant components of the vector …eld, ~v (x ) ; in

the dual basis vectors, e^ (x) : The controvariant and covariant components of
the vector …eld can be determined using Eq. (16.9)
a
~v (x) e^b (x) = v a (x) eâ (x) e^b (x) = v a (x) b = v b (x) : (16.11)
Similarly
va (x) = ~v (x) eâ (x) : (16.12)
Einstein’s summation convention: whenever an index occurs twice in an
expression, once as subscript and once as a superscript, imply a summation over
the index. An index should not occur more than twice. For example, according
to Einstein’s summation convention, the summations in Eq. (16.8) and (16.10)
can be expressed
~v (x ) = v (x ) e^ (x ) (16.13)
and
~v (x ) = v (x ) e^ (x ) ; (16.14)
respectively.
In…nitesimal vector separation: Consider two points P and Q on the
Minkowski spacetime with coordinates x and x + dx ; where dx is none zero
for all , then the in…nitessimal vector separation between these two points is
given by
d~s = e^ (x) dx (16.15)
The metric function: the inner product of the in…nitessimal vector sepa-
ration
ds2 = d~s d~s = e^ (x ) dx e^ (x ) dx = e^ (x ) e^ (x ) dx dx ) ds2 = g (x) dx dx ;
where
g (x ) = e^ (x ) e^ (x ) (16.16)
is the know as the covariant metric function. For the Minkowski spacetime the
local values for the covariant metric function are given by
2 3
1 0 0 0
6 0 1 0 0 7
G = [g ] = 64 0 0
7: (16.17)
1 0 5
0 0 0 1
The controvariant metric function given by
g (x ) = e^ (x ) e^ (x ) (16.18)
can be determined from the condition
g g = (16.19)
For the Minkowski spacetime under Lorentz transformation the local values for
the controvariant metric function are given by
2 3
1 0 0 0
6 0 1 0 0 7
G 1 = [g ] = 6 4 0 0
7 = G = [g ] : (16.20)
1 0 5
0 0 0 1
where G 1 is the inverse of the matrix G.

Lowering and raising indices: Consider the Controvariant form of the co-
ordinates of a point on the Minkowski spacetime, x ; the covariant coordinates,
x are determined by
2 32 3 2 3
1 0 0 0 ct ct
6 0 1 0 0 7 6 7 6 7
x =g x =6 76 x 7 = 6 x 7 (16.21)
4 0 0 1 0 54 y 5 4 y 5
0 0 0 1 z z
similarily
2 32 3 2 3
1 0 0 0 ct ct
6 0 1 0 0 7 6 x 7 6 x 7
x =g x =6
4 0
76 7=6 7 (16.22)
0 1 0 54 y 5 4 y 5
0 0 0 1 z z
Therefore, the metric for Lorentz transformation can raise or lower the indices.
Scalar-product: The scalar product of two vectors ~v and ~u in the the
Minkowski spacetime is given by
~v ~u = v e^ u e^ = v u e^ e^ = v u =v u (16.23)
The four velocity: In the Minkowski spacetime the trajectory of a particle

form the worldline (a curve on the manifold). This curve can be de…ned in
terms of some parameter. For a massive particle this parameter can be the
proper time, ; which is de…ned as
2
ds
= c2 ; (16.24)
d
where ds is an in…nitesimal displacement on the worldline. The worldline can
then be de…ned in terms of the proper time using the coordinates xa ( ) : The
four velocity, ua ( ), of a particle then is the tangent vector on the worldline.
dxa
~u ( ) = ua~ea = ~ea (16.25)
d
and the length of this tangent vector
2
ds
u( ) u( ) = = c2 (16.26)
d
or
dxa d (ct) dx1 dx2 dx3
[ua ] = = ; ; ; : (16.27)
d d d d d
Recalling that
d dt
dt = q )d = (16.28)
u2 u
1 c2
where
1
u =q (16.29)
u2
1 c2
we can write the four velocity
dxa dx1 dx2 dx3

[ua ] = = u c; ; ; = u [c; ~u] (16.30)
d dt dt dt
2 0 3 2 3
u uc
6 u1 7 6 u ux 7
) 6
4 u2
7=6 7
5 4 u uy 5 :
u3 u uz
The four-momentum of a particle: Suppose a particle (e.g. the Alien

in Fig. 16.1) is described by the four-velocity
dxa dx1 dx2 dx3

~u = ua~ea = ~ea = u c; ; ; = u [c; ~u] (16.31)
d d d d
as measured by an observer on S frame. Let the rest mass of the particle, that
I prefer to call it the "proper mass", be m0 . The proper mass is the mass
measured by an observer moving with the same velocity of the particle (the
IIF). The four momentum, P~ , on the S inertial frame is de…ned in terms of the
proper mass (rest mass)
a
dx dx1 dx2 dx3
P~ = pa~ea = m0 ua~ea = m0 = u m0 c; m0 ; m0 ; m0 = u [m0 c; m0 ~u]
d d d d
(16.32)
Note that here ~u represent the three velocity. Suppose we de…ne the rest mass
energy which I also prefer to call it the "Proper energy" as
E0 = m0 c2 ; (16.33)
the four momentum can be expressed as
E0
[pa ] = u ; m0 ~u (16.34)
c
or
E
P~ = [pa ] = ; p~ ; (16.35)
c
where p~ is the three-momentum and
E0 m0 c2
E=q =q (16.36)
u2 2
1 c2 1 uc2
is the relativistic energy of the particle as measured by an observer on the S
frame and
m0 ~u
p~ = u m0 ~u = q : (16.37)
2
1 uc2
is the relativistic momentum of the particle (the three-momentum). In Eq.
(16.32), we note that the magnitude of the four momentum
2
E0
P~ P~ = p p = m20 ua ua = m20 c2 = : (16.38)
c
Using the metric tensor one can also write
P~ P~ = p ~e p ~e = p p =p p
2 32 3
1 0 0 0 p0
6 0 1 0 0 7 6 1 7
= p0 p1 p2 p3 6 7 6 p2 7
4 0 0 1 0 54 p 5
0 0 0 1 p3
2 0 3
p
6 p1 7 2 2 2 2
= p0 p1 p2 p3 6 7
4 p2 5 = p
0
p1 p2 p3
p3
2 2
E E
) P~ P~ = p~ p~ = p2 : (16.39)
c c
From these two expressions one easily …nd

2 2 q
E E0 1
p2 = )p= E2 E02 : (16.40)
c c c
This is the magnitude of the three-momentum in special theory of relativity

that you may have seen in Intro physics or modern physics classes.
16.2 Relativistic wave equation for spin-0 particles-

the Klein-Gordon equation
We recall from none relativistic quantum mechanics the 3-diemensional Schrödinger
equation
@ ~2 @ ^ (x; y; z; t) ;
i~ (x; y; z; t) = 52 +V (x; y; z) (x; y; z; t) ) i~ (x; y; z; t) = H
@t 2m0 @t
(16.41)
where
^ = i~ @ = ~2
H 52 +V (x; y; z) (16.42)
@t 2m0
is the energy operator. In terms of the momentum operator
@ @ @
p^x = i~ ; p^y = i~ ; p^z = i~
@x @y @z
one can write for a free particle

! !
^ = ic~ @ =
H
1
p^2 + p^2y + p^2y =
p^ p^
: (16.43)
@ct 2m0 x 2m0
which leads to
@ ^
H @ E
i~ (x; y; z; t) = (x; y; z; t) ) i~ (x; y; z; t) = (x; y; z; t)
@ct c @ct c
(16.44)
where
!
p !
p p2
E= =
2m0 2m0
for a free particle. We note that
2 2
@ @ E E @ E
i~ (x; y; z; t) = i~ (x; y; z; t) = i~ (x; y; z; t) = (x; y; z; t)
@ct @ct c c @ct c
" #
2 2
@ E
) i~ (x; y; z; t) = 0 (16.45)
@ct c
16.2. RELATIVISTIC WAVE EQUATION FOR SPIN-0 PARTICLES-THE KLEIN-GORDON EQUATION389
For a free particle for none relativistic case, we have

1
E= p2 + p2y + p2y
2m0 x
so that one …nds
" #
@
2 !
p !p
2
i~ (x; y; z; t) = 0
@ct 2m0 c
However, for a relativistic case, using the relation from previous section for the
relativistic energy, rest-mass energy, and the three-momentum, we have
2 2 2
E E0 E
p2 = = m20 c2 ) = m20 c2 + !
p !
p
c c c
the Schrödinger equation for a free particle becomes
" #
2
@ 2 2 ! !
i~ m0 c p p (x; y; z; t) = 0
@ct
" #
2
@ ! !
) i~ p p (x; y; z; t) = m20 c2 (x; y; z; t) : (16.46)
@ct
Now replacing the momentum operator

2 2 2
! ! ! @ @ @
p !
p ! p^ p^ = i~ + i~ + i~ (16.47)
@x @y @z
we …nd
" #
2 2 2 2
@ @ @ @
i~ i~ i~ i~ (t; x; y; z) = m20 c2 (t; x; y; z) :
@ct @x @y @z
(16.48)
Using the notation introduced in the previous section, one can rewite this equa-
tion as
p^ p^ (x ) = m20 c2 (x ) (16.49)
where
x ! x0 ; x1 ; x2 ; x3 = (ct; x; y; z)
@ @ @ @ @ @ @ @
p^ ! p^0 ; p^1 ; p^2 ; p^3 = i~ ; ; ; = i~ ; ; (16.50)
;
@ (ct) @x @y @z @x0 @x1 @x2 @x3
Equation 16.49) is known as the Klein-Gordon equation for a free particle which
can also be put in the form
1 @2 @2 @2 @2 m20 c2
+ (t; x; y; z) = 0
c2 @t2 @x2 @y 2 @z 2 ~2
1 @ 2 (~r; t) m20 c2
) 52 (~r; t) = (~r; t) (16.51)
c2 @t2 ~2
which a wave equation with additional term m20 c2 =~2 :

The commutation relation: For a relativistic quantum mechanics, we want
to …nd the commutation relation for position and momentum
@
[^
p ; x ] = i~ [^
p ; x ] = i~ ;x : (16.52)
@x
Using the metric

x =g x (16.53)
Problem 1
Problem 1
(a) Show that the Klein-Gordon equation is invariant under Lorentz transfor-
mation.
(b) Show that the solution to the Klein-Gordon equation is given by
i i i
(~r; t) = exp p^ x = exp p^0 x0 p~ ~r = exp (~
p ~r Et)
~ ~ ~
(16.54)
Upon substituting the solution
i
(~r; t) = exp (~
p ~r Et) (16.55)
~
into the Klein-Gordon equation
1 @ 2 (~r; t) m20 c2
52 (~r; t) = (~r; t) (16.56)
c2 @t2 ~2
we …nd
q
p2 1 E2 m20 c2
(~r; t) + (~r; t) = (~r; t) ) E = c m20 c2 + p2 (16.57)
~2 c2 ~2 ~2
This shows that there existsd solutions both for positive and negative energies.
As you would probably see (if you go into high nergy particle physics) in the
future, the solutions giving negative energy are physically connected with an-
tiparticles. Since antiparticles can indeed be observed in nature, we have already
obtained an indication of the value of extending the nonrelativistic quantum
theorey to more genral relativistic quantum theory.
The four current and the probability density:
The commutation relation: For a relativistic quantum mechanics, we want
to …nd the commutation relation for position and momentum
@
[^
p ; x ] = i~ [^
p ; x ] = i~ ;x : (16.58)
@x
16.3. RELATIVISTIC WAVE EQUATION FOR SPIN-1/2 PARTICLES-THE DIRAC-EQUATION391
Using the metric

x =g x (16.59)
we may write
@
[^
p ; x ] = i~ ;g x : (16.60)
@x
Then using the wavefunction, (x ) ; we may write
@ @ @ (x )
[^
p ;x ] (x ) = i~ ;g x (x ) = i~ (g x (x )) g x
@x @x @x
(16.61)
so that using the product rule, one can write
@g @x @ (x ) @ (x )
[^
p ;x ] (x ) = i~ x (x ) +g (x ) +g x g x (16.62)
@x @x @x @x
@g @x
) [^
p ;x ] (x ) = i~ x (x ) +g (x ) : (16.63)
@x @x
We recall the metric elements for the Minkowski spacetime, are constant
2 3
1 0 0 0
6 0 0 7
[g ] = 6
1 0 7 ) @g = 0; (16.64)
4 0 0 1 0 5 @x
0 0 0 1
which leads to
@x
[^
p ;x ] (x ) = i~g (x ) = i~g (x ) = i~g (x ) (16.65)
@x
so that the relativistic commutation relation becomes
[^
p ; x ] = i~g : (16.66)
Note that the metric tensor is symmetric.
16.3 Relativistic wave equation for spin-1/2 particles-

the Dirac-equation
Chapter 17
Intro to quantum
informatics
Quantum information and quantum computation is one of recently emerged

and exciting …eld of applied physic. It vast and can not be covered with a
few lectures. Here my goal it to provide you with the fundamental concepts
that you may use as a bridge for further exploration in this most exciting and
fascinating application of quantum mechanics in information communication
and processing.
17.1 Quantum bits and quantum entanglement

Quantum bits
Single Qubit
In this electronic age it is a fact that we all have heard about bits from
the memory of a computer measured in Terabits(Tb), Gigabits (Gb), Megabits
(Mb) to its speed measured in Terabits per second (Tbps), Gigabits per second
(Gbps), Megabits per seconds (Mbps). These refers to the amount of informa-
tion that can be stored and the amount of information that can be transmitted
or manipulated in one second electronically. The bit is the fundamental concept
of classical computation and classical information. Quantum computation and
quantum information are built upon an analogous concept, the quantum bit,
or qubit for short. The concept of the qubit was unknowingly introduced by
Stephen Wiesner in 1983. Just as a classical bit has a state-either 0 or 1- a
quantum bit has also a state. The two possible states for a qubit are j0i and
j1i. But quantum mechanics tells us there is what we call the superposed state
j i = c0 j0i + c1 j1i : (17.1)
....the Schrödinger’s cat.

Schrödinger’s cat
393
394 CHAPTER 17. INTRO TO QUANTUM INFORMATICS
Figure 17.1: From Wikipedia
Schrödinger’s cat: a cat, a ‡ask of poison, and a radioactive source are placed
in a sealed box. If an internal monitor detects radioactivity (i.e. a single atom
decaying), the ‡ask is shattered, releasing the poison that kills the cat. The
Copenhagen interpretation of quantum mechanics implies that after a while, the
cat is simultaneously alive and dead. Yet, when one looks in the box, one sees the
cat either alive or dead, not both alive and dead. This poses the question of when
exactly quantum superposition ends and reality collapses into one possibility or
the other.
If we associate j0i to being the cat dead and j1i to being the cat alive, in the
classical world cat can be either alive (state j0i) or dead (state j1i). However,
in the quantum world, the cat can be both dead and alive at the same time...
the superposed state.
In general a qubit state is a unit vector in a two-dimensional complex vector
space given by Eq. (17.1), where
2 2
jc0 j + jc1 j = 1 (17.2)
Physically a qubit can be realized in di¤erent systems. Some of these include

the two di¤erent polarization of a photon, the alignment of a nuclear spin in a
uniform magnetic …eld, and the two states of an electron orbiting a two-level
atom we studied.
The Block Sphere: is a unit radius sphere used to represent a qubit. This
sphere though can not be generalized to multi qubits. Since a qubit is a nor-
malized vector and c0 and c1 are in general complex quantities, we can write
j i = ei cos j0i + sin ei' j1i ; (17.3)

2 2
17.1. QUANTUM BITS AND QUANTUM ENTANGLEMENT 395
Figure 17.2: The Stern-Gerlack (Single qubit)
which can also be expressed as
j i = cos j0i + sin ei' j1i ; (17.4)

2 2
since the factor ei does not bring any physical signi…cance. Here and ' are
the usual spherical coordinates (0 ; 0 ' 2 ). A point on this sphere
represent a qubit. For example for ' = 0 and = , we …nd
j i = j1i : (17.5)
Is there a Paradox? there are an in…nite number of points on the unit sphere,
so that in principle one could store an entire text of Shakespeare in the in…nite
binary expansion of : That is not possible. We may ask is there a paradox
here? The answer is no. Because we get either j0i or j1i when we conduct
a measurement. Furthermore, measurement in quantum mechanical system
changes the state of the system. For example if we make a measurement and
the result of the measurement is 0, then the post measurement state of the
qubit would be j0i : Why does this type of collapse occur? Nobody knows. This
behavior is simply one of the fundamental postulates of quantum mechanics.
Two qubits
We consider a two qubit state as this state partly a fundamental roll in
specially quantum communications. A two qubits state is given by
j i = c00 j00i + c01 j01i + c10 j10i + c11 j11i ; (17.6)
with the normalization condition
1
X 2 2 2 2 2
jcij j = jc00 j + jc01 j + jc10 j + jc11 j = 1: (17.7)
ij=0
Figure 17.3: The Block sphere
Such kind of state can be generated in the interaction of two coupled two-levels
atomic systems interacting with two photons or in parametric down conversion.
In two coupled two-level atomic systems, j00i can be associated with both atoms
2
in the ground state with probability jc00 j , j01i with the …rst atom in the ground
2
state and the second atom in the excited state with probability jc01 j ; j10i with
the …rst atom in the excited state and the second atom in the ground state
2
with probability jc10 j ; and j11i can be associated with both atoms in the ex-
2
cited state with probability jc11 j : In parametric down conversion a none linear
medium where the interaction of the …eld of the, E ~ of the electromagnetic waves
that of the order of E 2 ; a single photon can be splitted into two photons. These
two down converted photons can have same frequency but di¤erent polarization.
If we associate the x-polarization to j0i and y-polarization to j1i ;the two down
converted can emerge from the none linear medium in a state j00i both photons
2
x-polarized with probability jc00 j , j01i with the …rst photon x-polarized and
2
the second photon y-polarized with probability jc01 j ; j10i with the …rst photon
2
y-polarized and the second photon x-polarized with probability jc10 j ; and j11i
2
can be associated with both photons y-polarized with probability jc11 j :
For a two qubit system, we could measure just a subset of the qubit. Mea-
surements in Quantum mechanics are represented by projection operators. In
our two qubits state if we are measuring a subset of the qubits, we could mea-
sure a state j0i with outcome of 0, or a state j1i with outcome of 1: These
17.1. QUANTUM BITS AND QUANTUM ENTANGLEMENT 397
Figure 17.4: Parametric down conversion (two qubits)
measurement action represented by the projection operators
P^0 = j0i h0j (17.8)
and
P^1 = j1i h1j ; (17.9)
respectively. Suppose we measured the …rst qubit by measuring the state of the
…rst entity in the system (…rst atom or …rst photon) and the outcome is 0. We
may describe this measurement and the resulting new state of the system after
the measurement j i as n o
j i = T r1 P^0 j i (17.10)
where T r1 refers to the trace over all states of the …rst entity. Using Eqs. (17.6)
and (17.8), we have
j i = T r1 fj0i h0j [c00 j00i + c01 j01i + c10 j10i + c11 j11i]g (17.11)
Noting that in each ket vectors the …rst entry is for the …rst entity and the
second entry is for the second entity in the system and also the states that
belong to one entity are orthogonal to the state that belong to another entity
in the system, for
j i = T r1 fc00 j0i h0j 00i + c01 j0i h0j 01i + c10 j0i h0j 10i + c11 j0i h0j 11ig
(17.12)
we may write
j i = T r1 fc00 j00i + c01 j01ig (17.13)
Now tracing over the states of the …rst entity
j i = c00 h0j 00i + c01 h0j 01i = c00 j0i + c01 j1i (17.14)
Since after the measurement of the state of the …rst entity the probability that
the remaining entity be in the state j0i or j1i must be one
2 2
jc00 j + jc01 j = 1 (17.15)
the new state in Eq. (17.14) must be normalized
c00 j0i + c01 j1i

j i= q
2 2
jc00 j + jc01 j
In An important two qubit state is the Bell state or EPR pair

1
j i = p (j00i + j11i) ; (17.16)
2
which is the key in quantum teleportation. The Bell state has the property
that upon measuring the …rst qubit, one obtains two possible outcomes 0 with
probability of 1/2 leaving the state j00i
1 1 1 1
h0 j i = p (h0 j00i + h0 j11i) = p (h0 j00i) = p (h0 j0i j0i) = p j0i ;
2 2 2 2
or 1 with probability of 1=2 leaving the state j11i
1 1 1 1
h1 j i = p (h1 j00i + h1 j11i) = p (h1 j11i) = p (h1 j1i j1i) = p j1i :
2 2 2 2
As a result the measurement on the second qubit results in the same value
as the measurement of the …rst qubit. That is the measurement outcomes are
correlated.
N qubits
The computational basis states of the system of n qubits are of the form
jx1 x2 x3 :::xn i ; and so a quantum state of such a system is speci…ed by 2n
amplitudes. For n = 500 this number is larger than the estimated number of
atoms in the universe! Trying to store all these complex numbers would not
possible on any conceivable classical computer.
Analogous to the way a classical computer is built from an electrical circuit
containing wires and logic gates, a quantum computer is built from a quantum
circuit containing wires and elementary quantum gates to carry around and
manipulate the quantum information. We shall consider here the basic one
qubit and two qubit quantum gates.
17.2 Single Qubit gate

Those of you who took Algebra based introductory physics II you have been in-
troduced to the basic logic gates in digital electronic. Logic gates are the build-
ing blocks for classical information transmission, manipulation, and processing.
17.2. SINGLE QUBIT GATE 399
Figure 17.5: Classigan sigle bit gate (the Not gate)
Classical single bit gate is the not gate. Its job is to change 0 to 1 or 1 to 0.
There are three basic single qubit gates. These are the quantum Not gate (the
X gate), the Z gate, and the Hadamard gate. Each of these gates transforms a
qubit di¤erently.
The quantum Not gate (X gate):
X j i = X [c0 j0i + c1 j1i] = c1 j0i + c0 j1i ;
The Z gate:
Z j i = Z [c0 j0i + c1 j1i] = c0 j0i c1 j1i ;
The Hadamard gate (H gate):

1 1
H j i = X [c0 j0i + c1 j1i] = c0 p (j0i + j1i) + c1 p (j0i j1i) ;
2 2
Homework #1: Can you design and describe a physical system that can be
used as any one of the di¤ erent quantum not gates we discussed above.
In quantum mechanics it is convenient to represent states and operators
using matrices. We already know that state ket vectors are represented by
column matrix and state bra vectors by row matrix. Thus the qubit state
j i = c0 j0i + c1 j1i ; (17.17)
can expressed using matrices by the column matrix

c0
j i! : (17.18)
c1
A single qubit gates are then represented by 2 2 matrices. The X, Y, and H
gates are then represented by the following matrices
0 1 1 0 1 1 1
X! ;Z ! ;H ! p : (17.19)
1 0 0 1 2 1 1
Generally matrices representing quantum gates must be unitary matrices
because the operations should leave the qubit normalized. For unitary matrices
M y = M 1 : Thus for the single qubit gates we must have
XX y = ZZ y = HH y = I; (17.20)
where X y ; Z y ; and H y are the transpose and conjugate matrices of X; Z; and H
and I is the identity matrix. This can be shown in general as follows
0 c0 c00
Hj i= )H = (17.21)
c1 c01
The normalization condition states that
2 2 c0
jc0 j + jc1 j = c0 c1 =1 (17.22)
c1
and
2 2 c00
jc00 j + jc01 j = c00 c01 = 1: (17.23)
c01
Noting that
y y y y
c0 c00 c0 c00
H = ) Hy =
c1 c01 c1 c01
) c0 c1 Hy = c00 c01 (17.24)
we can write
c00 c0 c0
c00 c01 = c0 c1 H yH = c0 c1 =1
c01 c1 c1
) H yH = I (17.25)
This proves that single qubit gates must be represented by a unitary matrices.
17.3. MULTIPLE QUBIT 401
17.3 Multiple Qubit
In classical computing the basic multiple bit gates are: And, OR, NAND, NOR,
EOR (Exclusive-or). The NAND gate is called the universal gate because any
function can be computed using a combination of NAND gates. The proto-
typical multi-qubit quantum gate is the controlled-NOT gate (CNOT). It has
two inputs and the …rst input is called the control qubit which decides the out
come of CNOT operation and the second input is called the target qubit. The
quantum logic symbol showing these inputs and outputs are shown in the …gure
below.
If the control qubit is set to 0 the target qubit remain unchanged and if the
control qubit is 1 the target qubit is ‡ipped. That means for
j00i CN OT
!; j00i (17.26)
j01i CN OT
!; j01i
j10i CN OT
!; j11i
j11i CN OT
!; j10i
The CNOT gate is represented by a 4 4 unitary matrix given by

2 3
1 0 0 0
6 0 1 0 0 7
UCN =6
4 0
7 (17.27)
0 0 1 5
0 0 1 0
Homework #2: Prove that the matrix representation of the CNOT gate is uni-
tary using the matrix representation for a two-qubit state
j i = c00 j00i + c01 j01i + c10 j10i + c11 j11i ; (17.28)
Can you design and describe a controlled not gate for real physical system.
17.4 Quantum Circuits

It is not hard to …gure out that any classical information processor is made of
classical circuits built from several single- and multi- bits gates connected by
electrical wiring. Generally we can say the same is true for quantum information
processor. It should be built from wired several single- and multi- qubits gates.
But the wiring does not necessarily be a physical wire; it may correspond to
instead to the passage of time, or perhaps to a physical particle such as photon
moving from one location to another through space. The following …gure repre-
sent a quantum circuit. It is read from left to right. It consist of three CNOT
gate and lines that represent wirings which are not necessarily a physical wiring.
This circuit swaps the states of the two qubit. That means if the …rst qubit
is jai and the second qubit is jbi ; the the circuit does the following
ja; bi Curcuit
! jb; ai :
We can easily understand if we use computational basis. For example let’s say
the control qubit is j0i and the target qubit is j1i so that the input state is
17.5. THE NO-CLONING THEOREM 403
Figure 17.6: Quantum Circuit
j0; 1i :
j0; 1i ! j0; 1i 1st CNOT (17.29)

nd
j1; 0i ! j1; 1i 2 CNOT
rd
j1; 1i ! j1; 0i 3 CNOT
There are a few features allowed in classical circuits that are not usually present
in quantum circuits. These are the following
1. Loops: feedback from one part of the quantum circuits to another is not
allowed. The circuit is acyclic unlike classical circuit.
2. Fanin: Classical circuits allow wires to be joined together, an operation

known as Fanin, with resulting single wire containing the bitwise OR of
the inputs. This operation is not reversible and therefore is not Unitary
so it is not allowed in quantum circuits.
3. Fanout: the inverse operation of Fanin where several copies of a bit are
produced is also not allowed in quantum circuits. Because quantum me-
chanics forbids the copying of a qubit.
In the following we shall prove that quantum mechanics forbids copying
qubits which commonly referred as no quantum cloning.
17.5 The no-cloning theorem

Suppose we have a quantum machine with two slots A and B. Slot A is the is
the data slot, starts out in an unknown but pure quantum state, j i. This is
the state which is to be copied into slot B, the target slot. We assume that the
target slot starts out in some standard pure state j i : Then the initial state
would then be
jIi = j i j i (17.30)
The quantum machine then performs some unitary operation, which we may
represent with operator U; and let’s say it has carried out the quantum cloning
(quantum copying) and results the …nal state
jF i = j i j i (17.31)
That means
U jIi = jF i ) U (j i j i) = j i j i (17.32)
Now let’s say the same quantum machine perform the cloning for another com-
pletely di¤erent quantum state j i : That means we put in a quantum state into
slot A that we want to copy into slot B which also, this time too, starts out in
same state j i ;
U jI 0 i = jF 0 i ) U (j i j i) = j i j i (17.33)
and
hI 0 j U y = hF 0 j ) (h j h j) U y = h j h j: (17.34)
Now taking the inner products of Eq. (17.32) and (17.34), we have
(h j h j) U y U (j i j i) = (h j h j) (j i j i) : (17.35)
We recall that operations in a quantum machine whether it is carried out with

single or multi qubit gates, it must be Unitary
U y U = 1:
Thus the above equation leads to
(h j i) h j i = h j i h j i : (17.36)
Noting that
h j i=1
we …nd
2
h j i = (h j i) ) h j i (1 h j i) = 0 ) h j i = 0 or h j i = 1:
(17.37)
There follows that quantum cloning is possible only for an orthonormal states.
That means either j i = j i or j i and j i are orthogonal. thus a quan-
tum cloning device can only clone states which are orthogonal to one another,
and therefore a general quantum cloning device is impossible. A potential
quantum cloner pcannot, for example, clone the qubit states j i = j0i and
j i = (j0i + j1i) 2 since these states are not orthogonal.
Ex. By using the quantum two-qubits gate (CNOT gate) show that
(a) The single qubit
j i = c0 j0i + c1 j1i (17.38)
can not be cloned
17.6. QUANTUM ENTANGLEMENT AND THE BELL STATES-EPR PAIRS405
(b) Also show that classical bits can be cloned using the quantum CNOT gate.
Sol:
(a) Let’s set the target qubit to j0i to which we are interested in copying our
single qubit on. The input state will then be written as
jIi = j i j0i = (c0 j0i + c1 j1i) j0i = (c0 j0; 0i + c1 j1; 0i) (17.39)
Then the operation of the CNOT gate leads to the output state given by
jOi = U j i j0i = (c0 U j0i j0i + c1 U j1i j0i) = (c0 j0i j0i + c1 j1i j1i)
) jOi = c0 j0; 0i + c1 j1; 1i (17.40)
Now if the state has been successfully copied to the target qubit, the
output state should have been
jOi = U j i j0i = j i j i (17.41)
which in fact is given by
jOi = (c0 j0; 0i + c1 j1; 1i) (c0 j0; 0i + c1 j1; 1i)

= c20 j00i + c0 c1 j01i + c1 c0 j10i + c21 j11i : (17.42)
This is obviously di¤erent from the output of the CNOT gate.
Controled-U gate: this is a natural extension of the controled-NOT gate

(CNOT). It has a single control qubit indicated by the line on a black dot, and
n target qubits indicated by the boxed U. if the control qubit is set to 0 then
nothing happens to the target qubits. If the control qubit is set to 1 then get
U is applied to the Target qubits.
Quantum Measurement: measurement is represented by a "meter" symbol.
Measurement is an operation that converts a single qubit state
j i = c0 j0i + c1 j1i
into a probabilistic classical bit M (distinguished from a qubit by drawing it

2
as a double-line wire), which is 0 with probability jc0 j and 1 with probability
2
jc1 j :
17.6 Quantum entanglement and the Bell states-

EPR pairs
Quantum entanglement is a property of a quantum mechanical state of a system
of two or more objects in which the quantum states of the constituting objects
are linked together so that one object can no longer be adequately described
without full mention of its counterpart — even though the individual objects
may be spatially separated. We may describe quantum entanglement, using

a quantitative approach. Consider two non-interacting systems 1 and 2, with
respective Hilbert spaces H1 and H2 . The Hilbert space of the composite system
is the tensor product
H12 = H1 H2 (17.43)
If system 1 is in state j 1i and system 2 in state j 2 i, the state of the composite
system is
j 12 i =j 1i j 2i (17.44)
In terms of a basis ji1 i for H1 and a basis jj2 i for H2 , the most general state of
the composite system in the H12 Hilbert space can be expressed as
X X
j 12 i = Cij ji1 i jj2 i = Cij ji1 ; j2 i : (17.45)
i;j i;j
If this state is separable, we have
Cij = Ci1 Cj2
which leads to
X X
j 12 i = Ci1 ji1 i Cj2 ji2 i ) j 12 i =j 1i j 2i (17.46)
i j
and the state is not an entangled state and there is no quantum entanglement
between system 1 and system 2. On the other hand, if the state is inseparable,
we have
Cij 6= Ci1 Cj2 (17.47)
and the state is an entangled state.
We consider a two particle system such as a two-photon or a two two-level
atoms systems. For these systems we may write i = 0; 1 and j = 0; 1 so that
the quantum state of the bipartite system can be written as
j 12 i = c00 j00i + c01 j01i + c10 j10i + c11 j11i : (17.48)
On the other hand using the quantum state for each particle
j 1i = c01 j0i + c11 j1i ; j 2i = c02 j0i + c12 j1i
we may write the bipartite state as a tensor product given by
j 12 i = (c01 j0i + c11 j1i) (c02 j0i + c12 j1i)

= c01 c02 j00i + c01 c12 j01i + c11 c02 j10i + c11 c12 j11i : (17.49)
The bipartite system is said to be in entangled state provided
c00 6= c01 c02 ; c01 6= c01 c12 ; c10 6= c11 c02 or c11 6= c11 c12
17.7. QUANTUM TELEPORTATION 407
The Bell states are one example of entangled quantum state of a bipartite sys-
tem.
Quantum Circuit for generating Bell States: This circuit consists of a H-
gate followed by CNOT gate. We recall that the H-gate takes a single qubit
described by the sate
j i = c0 j0i + c1 j1i (17.50)
and convert it into
c0 c1
j i = p (j0i + j1i) + p (j0i j1i) : (17.51)
2 2
For c1 = 0 then the H-gate gives
c0
j 1 iH = p (j0i + j1i) (17.52)
2
and for c0 = 0
c1
j= p (j0i j1i) :
2 iH (17.53)
2
These are the state which will be used as control qubit in the CNOT gate.
Therefore, for a target qubit j0i, the CNOT gate gives
c1
j 1 iH ! CN OT ! j = p (j00i + j11i)
00 i (17.54)
2
c1
j 2 iH ! CN OT ! j 10 i = p (j00i j11i) (17.55)
2
On the other hand for a target qubit of j1i, the CNOT gate gives
c1
j 1 iH ! CN OT ! j = p (j01i + j10i)
01 i (17.56)
2
c1
j 2 iH ! CN OT ! j 11 i = p (j01i j10i) (17.57)
2
These four states are maximally entangled state and they are known as Bell
states. Pairs of particles described by these kind of states are called Einstein–
Podolsky–Rosen (EPR) pair. In the next section we will study how such kind
of states can be used for something non-trivial, surprising, and a lot of fun-
quantum teleportation!
17.7 Quantum Teleportation

Quantum teleportation is a technique for moving quantum states around, even
in the absence of a quantum communications channel linking the sender of the
quantum state to the recipient. Here is how quantum teleportation works: Alice
and Bob met a long time ago. They are now living apart. During their time
together they have shared EPR pair. Let this EPR pair be
1
j 12 i = p (j00i + j11i) : (17.58)
2
Let the …rst entry (1) be the one Alice posses and the other entry (2) be the
one Bob posses. Alice has this information which is encrypted in a one qubit
state
j 3 i = c0 j0i + c1 j1i : (17.59)
She has absolutely no clue what is about and quantum mechanics forbids her
from knowing what it is about. Because she has to make some kind of measure-
ment in order to know about it and we know quantum measurement changes
or collapse the state. She can not send a qubit in a classical channel since it
takes in…nite space. So how can she deliver the message to Bob? This is when
quantum teleportation works. The circuit for quantum teleportation is shown
in the …gure below.
Operation one: Alice send her share of the EPR pair through a controled-
NOT gate using the one qubit encrypted information as E a control qubit. If
I
we denote the out put state of this operation by 123 The outcome of this
operation is described by the state
E 1
I
123 = UCN j 12 i j 3 i = UCN p (j00i + j11i) (c0 j0i + c1 j1i)
2
E c0 c1
I
) 123 = p (j00i + j11i) j0i + p (j10i + j01i) j1i : (17.60)
2 2
Operation two: Alice then send the one qubit which she used as control Equbit
into an H-gate. If we denote the output state of this operation by II 123 , we
have
E E c0 c1
II I
123 = H 123 = H p (j00i + j11i) j0i + p (j10i + j01i) j1i
2 2
c0 1 c1 1
= H p (j00i + j11i) p (j0i + j1i) + p (j10i + j01i) p (j0i j1i)
2 2 2 2
(17.61)
c0 c1
= (j00i + j11i) (j0i + j1i) + (j10i + j01i) (j0i j1i) :
2 2
If we rearrange this expression to write it in the form
E c c0
II 0
123 = (j00i j0i + j11i j0i) + (j00i j1i + j11i j1i)
2 2
c1 c1
+ (j10i j0i + j01i j0i) (j10i j1i + j01i j1i) : (17.62)
2 2
17.7. QUANTUM TELEPORTATION 409
E c0 c0 c0 c0
II
) 123 = j00i j0i + j11i j0i + j00i j1i + j11i j1i
2 2 2 2
(17.63)
c1 c1 c1 c1
+ j10i j0i + j01i j0i j10i j1i j01i j1i :
2 2 2 2
Noting that the …rst entry (1) and encrypted qubit belongs to Alice Station,
grouping these terms into groups of qubits belonging to Alice and Bob, we can
rewrite this in the form
E 1
) II 123 = fj00i c0 j0i + j00i c1 j1i + j10i c0 j1i + j10i c1 j0i + j01i c0 j0i j01i c1 j1i
2
+ j11i c0 j1i j11i c1 j0ig : (17.64)
1 E
II
) 123 =
fj00i c0 j0i + j00i c1 j1i + j10i c0 j1i + j10i c1 j0i
2
+ j01i c0 j0i j01i c1 j1i + j11i c0 j1i j11i c1 j0ig : (17.65)
1
j 123 i = fj00i (c0 j0i + c1 j1i) + j10i (c0 j1i + c1 j0i)
2
+ j01i (c0 j0i c1 j1i) + j11i (c0 j1i c1 j0i)g : (17.66)
The state in Eq. (17.66) represent the three partite state after the CNOT and
Haddamard operation.
Operation three: Alice conduct measurement to determine the states of the
two entities in her station and must sent the result to Bob. She can do that
though a classical channel. We recall that quantum measurement is represented
by an operator (in the diagram by the meter symbol). The measurement can re-
sult in j00i ; j01i ; j10i ; or j11i which results in di¤erent qubit states summarized
below 8 9
>
> Measured outcome Bob’s qubit >
>
>
> >
< j00i h00 j 123 i = 12 (c0 j0i + c1 j1i) >
=
1
j10i h10 j 123 i = 2 (c0 j1i + c1 j0i)
>
> >
>
> j01i h01 j 123 i = 12 (c0 j0i c1 j1i) > >
>
: 1 ;
j11i h11 j 123 i = 2 (c0 j1i c1 j0i)
Operation four: For a successful quantum teleportation (faithful transmis-
sion of data or perfect …delity of the teleporation), Bob must recover the exact
state of the qubit
j 3 i = c0 j0i + c1 j1i : (17.67)
in his station. In order to do that he must know the outcome of Alice’s measure-
ment. It is this fact which prevents teleportation from being used to transmit
information faster than light. …rst term in this expression has Alice’s qubits in
the state j00i, and bob’s qubit in the state c0 j0i + c1 j1i which is the original
state Alice wanted to deliver to Bob.
(i) Alice’s Measurement j00i, Bob would recover the qubit with out any
additional gate
(ii) Alice’s Measurement j10i ;Bob uses and X gate
X (c0 j1i + c1 j0i) = c0 j0i + c1 j1i (17.68)
(iii) Alice’s Measurement j01i ;Bob uses and Z gate
Z [c0 j0i + c1 j1i] = c0 j0i c1 j1i ; (17.69)
(iV) Alice’s Measurement j11i ;Bob uses X followed by Z gates
ZX (c0 j1i c1 j0i) = Z (c1 j1i c0 j0i) = c0 j0i + c1 j1i ; (17.70)
17.8 Quantum analyses of entanglement

The Bell states are are good examples of two-partite system with the maximal
entanglement. It is important to know how the degree of entanglement for two
or more partite system can be described quantitatively. Here we shall discuss
two ways commonly used to quantify entanglement in a two-partite system.
These are using the von Neumann entropy and the Concurrence. Both the
von Neumann entropy and the concurrence directly or indirectly depend on
the quantum density operators describing the system. It is important to brie‡y
discuss the quantum density operator.
The density operator: In quantume mechanical problems, a probability dis-
tribution for the system comes from the statistical or density operator. Suppose
we know that the system is in state j i, and operator A^ has the expectation
value D E
A^ = h j A^ j i : (17.71)
QM
But we typically do not know that we are in j i : We only have a probability

Pn for being in the state so we must perform an ensemble average as well
( ) ( )
D E X X X
^
A = ^
Pn h n j A j n i = T r ^
Pn j n i h n j A = T r Pn A^ j ni h nj
QM ensemble n n n
(17.72)
D E on
) A^ = T race Â^ : (17.73)
QM ensemble
where T r refers to the trace of the matrix elements and

X
^= Pn j n i h n j (17.74)
n
is the density operator for the ensemble. For an ensemble in which
1 n=1
Pn = (17.75)
0 n 6= 1
17.8. QUANTUM ANALYSES OF ENTANGLEMENT 411
the density operator is given by
^=j 1i h 1j (17.76)
and the state is called a pure state. For a pure state it can be shown, from the
condition that the total probability is one,
( )
X
T r f^g = T r Pn j n i h n j = 1 (17.77)
n
it can be shown that

T r ^2 = 1 (17.78)
Homework #3: Show that for a pure state
T r ^2 = T r f^g = 1 (17.79)
From Wikipedia, the free encyclopedia...

The ensemble interpretation, or statistical interpretation of quantum me-
chanics, is an interpretation that can be viewed as a minimalist interpretation;
it is a quantum mechanical interpretation that claims to make the fewest assump-
tions associated with the standard mathematical formalization. At its heart, it
takes to the fullest extent the statistical interpretation of Max Born for which he
won the Nobel Prize in Physics. The interpretation states that the wave function
does not apply to an individual system – or for example, a single particle – but
is an abstract mathematical, statistical quantity that only applies to an ensemble
of similarly prepared systems or particles. Probably the most notable supporter
of such an interpretation was Albert Einstein:
The attempt to conceive the quantum-theoretical description as the complete
description of the individual systems leads to unnatural theoretical interpreta-
tions, which become immediately unnecessary if one accepts the interpretation
that the description refers to ensembles of systems and not to individual systems.
— Albert Einstein
EI: A pure state describes the statistical properties of an ensemble of similarly
prepared systems.
17.8.1 Entanglement by the entropy

Using the von Neumann entropy, the entanglement (E), of a bipartite system
is given by
E = T r [î log2 î ] ; (17.80)
where
î = T rj îj (17.81)
is the density operator for one of the parties obtained from the joint density
operator îj by tracing over all states of the other party in the bipartite system.
For maximal entanglement, E = 1 and for minimal entanglement (or no enat-

nglement) E = 0. If k are the eigen values of the density operator î then the
von Neumann’s de…nition can be re-expressed as
X
E= k log2 ( k ) : (17.82)
k
Ex. 1 Consider two photons (photon 2 and Photon 3) which are polarization
entangled. The state of these photons is described by the ket vector
j 23 i = c1 jh2 ; v3 i + c2 jv2 ; h3 i
where c1 and c2 are in general complex variables.
(a) Find the bra vector (h 23 j).
(b) Find the density operator ~23 :
(c) Determine
^2 = T r3 (^23 ) and ^3 = T r2 (^23 ) :
(d) Calculate the entanglement, E, using the von Neumann entropy.
(e) Let the variables c1 and c2 are real and given by
c1 = sin ( ) ; c2 = cos ( ) :
Analyze the degree of the entanglement applying your result in part d (i.e.
plot E vs. using Mathematica). When the two photons are maximally
or minimally entangled.
Sol:
(a) The bra vector for the state described by the ket vector
j 23 i = c1 jh2 ; v3 i + c2 jv2 ; h3 i
is give by
h 23 j = [c1 jh2 ; v3 i + c2 jv2 ; h3 i] = (c1 jh2 ; v3 i) + (c2 jv2 ; h3 i)

)h 23 j = c1 (jh2 ; v3 i) + c2 (jv2 ; h3 i)
h 23 j = c1 hh2 ; v3 j + c2 hv2 ; h3 j
(b) The density operator, ~23 ; is given by
~23 = j 23 i h 23 j :
Using
j 23 i = c1 jh2 ; v3 i + c2 jv2 ; h3 i
and
h 23 j = c1 hh2 ; v3 j + c2 hv2 ; h3 j
we …nd
~23 = (c1 jh2 ; v3 i + c2 jv2 ; h3 i) (c1 hh2 ; v3 j + c2 hv2 ; h3 j)
) ~23 = c1 c1 jh2 ; v3 i hh2 ; v3 j + c2 c1 jv2 ; h3 i hh2 ; v3 j + c1 c2 jh2 ; v3 i hv2 ; h3 j

+c2 c2 jv2 ; h3 i hv2 ; h3 j :
2
) ~23 = jc1 j jh2 ; v3 i hh2 ; v3 j + c2 c1 jv2 ; h3 i hh2 ; v3 j + c1 c2 jh2 ; v3 i hv2 ; h3 j
2
+ jc2 j jv2 ; h3 i hv2 ; h3 j :
(c) We note that

^2 = T r3 (^23 ) :
means we need to trace the joint density operator obtained in part (b)
over the states of photon 3
^2 = T r3 (^23 ) = hv3 j ^23 jv3 i + hh3 j ^23 jh3 i :
2
) ^2 = jc1 j hv3 j jh2 ; v3 i hh2 ; v3 j jv3 i + c2 c1 hv3 j jv2 ; h3 i hh2 ; v3 j jv3 i
2
+c1 c2 hv3 j jh2 ; v3 i hv2 ; h3 j jv3 i + jc2 j hv3 j jv2 ; h3 i hv2 ; h3 j jv3 i
2
+ jc1 j hh3 j jh2 ; v3 i hh2 ; v3 j jh3 i + c2 c1 hh3 j jv2 ; h3 i hh2 ; v3 j jh3 i
2
+c1 c2 hh3 j jh2 ; v3 i hv2 ; h3 j jh3 i + jc2 j hh3 j jv2 ; h3 i hv2 ; h3 j jh3 i
We may rewrite this equation as
2
^2 = jc1 j hv3 j jv3 i jh2 i hh2 j hv3 j jv3 i + c2 c1 hv3 j jh3 i jv2 i hh2 j hv3 j jv3 i
2
+c1 c2 hv3 j jv3 i jh2 i hv2 j hh3 j jv3 i + jc2 j hv3 j jh3 i jv2 i hv2 j hh3 j jv3 i
2
+ jc1 j hh3 j jh2 i jv3 i hh2 j hv3 j jh3 i + c2 c1 hh3 j jh3 i jv2 i hh2 j hv3 j jh3 i
2
+c1 c2 hh3 j jv3 i jh2 i hv2 j hh3 j jh3 i + jc2 j hh3 j jh3 i jv2 i hv2 j hh3 j jh3 i :
so that taking into account that the polarization set of vectors for an
orthonormal set
hv3 j jh3 i = hv3 j jh2 i = 0; hh3 j jh2 i = hv3 j jv2 i = 0;
hv3 j jv3 i = hv2 j jv2 i = 1; hh3 j jh3 i = hh2 j jh2 i = 1;
the density operator becomes
2 2
^2 = jc1 j jh2 i hh2 j + jc2 j jv2 i hv2 j :
As an exercise following the same procedure determine

^3 = T r2 (^23 ) :
Short way: We note that for pure state the density operator is given by
~23 = j 23 i h 23 j :
so that
^2 = T r3 (^23 ) = hv3 j ^23 jv3 i + hh3 j ^23 jh3 i
becomes
^2 = hv3 j 23 i h 23 j v3 i + hh3 j 23 i h 23 j h3 i
2 2
^2 = jhv3 j 23 ij + jhh3 j 23 ij
Noting that
hv3 j 23 i = c1 hv3 j h2 ; v3 i + c2 hv3 j v2 ; h3 i = c1 jh2 i
hh3 j 23 i = c1 hh3 j h2 ; v3 i + c2 hh3 j v2 ; h3 i = c2 jv2 i

we may write
2 2 2 2
jhv3 j 23 ij = jc1 j jh2 i hh2 j ; jhh3 j 23 ij = jc2 j jv2 i hv2 j
so that
2 2
^2 = jc1 j jh2 i hh2 j + jc2 j jv2 i hv2 j :
(d) The entanglement, E, using the von Neumann entropy is given by
E= T r [^2 log2 ^2 ] ;
or X
E= k log2 ( k) : (17.83)
k
where k are the eigenvalues of the density matrix ^2
hh2 j ^2 jh2 i hh2 j ^2 jv2 i

M= :
hv2 j ^2 jh2 i hv2 j ^2 jv2 i
Using the result in part (c), we can easily show that

2 2 2
hh2 j ^2 jh2 i = hh2 j jc1 j jh2 i hh2 j + jc2 j jv2 i hv2 j jh2 i ) hh2 j ^2 jh2 i = jc1 j
2 2
hh2 j ^2 jv2 i = hh2 j jc1 j jh2 i hh2 j + jc2 j jv2 i hv2 j jv2 i ) hh2 j ^2 jv2 i = 0
2 2 2
hv2 j ^2 jv2 i = hv2 j jc1 j jh2 i hh2 j + jc2 j jv2 i hv2 j jv2 i ) hv2 j ^2 jv2 i = jc2 j
2 2
hv2 j ^2 jh2 i = hv2 j jc1 j jh2 i hh2 j + jc2 j jv2 i hv2 j jh2 i ) hv2 j ^2 jv2 i = 0
so that
2
jc1 j 0
M= 2 :
0 jc2 j
and the eigenvalues of this matrix are
2 2
1 = jc1 j ; 2 = jc2 j :
Then the von Neumann entropy
X
E= k log2 ( k) : (17.84)
k
becomes
h i
2 2 2 2
E= jc1 j log2 jc1 j + jc2 j log2 jc2 j :
(e) For the case c1 and c2 are real and given by
c1 = sin ( ) ; c2 = cos ( ) :
the von Neumann entropy is calculated using Mathematica as follows:

Homework #5: Consider two polarization entangled photons (photon 2 and

Photon 3). The state of these photons is described by the ket vector
j 23 i = c1 jh2 ; h3 i + c2 jv2 ; v3 i
(a) Find the bra vector ( h 23 j).
(b) Find the density operator ~23 :

(c) Determine
^2 = T r3 (^23 ) and ^3 = T r2 (^23 ) :
(d) Calculate the entanglement, E, using the von Neumann entropy.

(e) Let the variables c1 and c2 are given by
c1 = cos ( ) ; c2 = i sin ( ) :
Analyze the entanglement applying your result in part d (i.e. plot E vs.
using Mathematica). When the two photons are maximally or minimally
entangled?Homework #4: Derive Eq. (17.82) from Eq. (17.80)
17.8.2 Entanglement by the Concurrence

For the case of discrete bipartite density matrix 23 ; the concurrence, C; is given
by
C = max f0; 1 2 3 4g ; (17.85)
in which the 0k s (with 1 = 2 = 3 = 4) are the square roots of the eigenval-

ues of the Hermitian matrix
~ = ^12 (^ 1y ^ 2y ) ^12 (^ 2y ^ 1y ) : (17.86)
where
^12 = j 12 i h 12 j
is the density operator and
^ 1y = i jj1 i hk1 j i jk1 i hj1 j
^ 2y = i jj2 i hk2 j i jk2 i hj2 j
are the Pauli single-qubit operators. Note that for two two-dimensional square
matrices A and B
a11 a12
A=
a21 a22
b11 b12
B=
b21 b22
the tensor product (A B) is given by
2 3
b11 b12 b11 b12
a11 a12 b11 b12 6 a11 b21 b22
a12
b21 b22 7
A B= =6
4
7
5
a21 a22 b21 b22 b11 b12 b11 b12
a21 a22
b21 b22 b21 b22
2 3
a11 b11 a11 b12 a12 b11 a12 b12
6 a11 b21 a11 b22 a12 b21 a12 b22 7
)A B=6
4 a21 b11
7
a21 b12 a22 b11 a22 b12 5
a21 b21 a21 b22 a22 b21 a22 b22
We recall the Pouli Spin Matrices
0 1 0 i 1 0
x = ; y = ; x =
1 0 i 0 0 1
for Spin-1/2 particle (e.g. an electron) with eigenstates j"i and j#i : The Corre-
sponding operators that generate the y matrix is given by
^ y = i j#i h"j i j"i h#j (17.87)
h"j ^ y j"i h"j ^ y j#i h"j (i j#i h"j i j"i h#j) j"i h"j (i j#i h"j i j"i h#j) j#i
) y = =
h#j ^ y j"i h#j ^ y j#i h#j (i j#i h"j i j"i h#j) j"i h#j (i j#i h"j i j"i h#j) j#i
(17.88)
h"j i j#i h"j j"i i h"j j"i h#j j"i h"j i j#i h"j j#i i h"j j"i h#j j#i
=
h#j i j#i h"j j"i i h#j j"i h#j j"i h#j i j#i h"j j#i i h#j j"i h#j j#i
0 i
) y =
i 0
Ex. 2 Consider two polarization entangled photons (Photon 2 and Photon 3)

described by the state vector
j 23 i = c1 jh2 ; v3 i + c2 jv2 ; h3 i
(a) Determine the Pauli single-qubit operators ^ 2y and ^ 3y
(b) Using the result in part (a) and in example 1 part (b), …nd the matrix
~ = ^23 ^ 2y ^ 3y ^23 ^ 3y ^ 2y :
and show that it is Hermitian.
(c) For the Hermitian matrix you obtained in part b …nd the eigenvalues and
then the concurrence.
(d) Once again let the variables c1 and c2 are real and given by
c1 = sin ( ) ; c2 = cos ( ) :
Analyze the degree of the entanglement applying your result for the con-
currence in part c (i.e. plot E vs. using Mathematica). Make sure that
the result agrees with what you obtained in Example 1 part e.
Sol:
(a) The Pauli single-qubit operators ^ 2y and ^ 3y can be expressed as
^ 2y = i jh2 i hv2 j i jv2 i hh2 j ; ^ 3y = i jh3 i hv3 j i jv3 i hh3 j
(b) We note that
^ 2y ^ 3y = (i jh2 i hv2 j i jv2 i hh2 j) (i jh3 i hv3 j i jv3 i hh3 j)

^ 3y ^ 2y = (i jh3 i hv3 j i jv3 i hh3 j) (i jh2 i hv2 j i jv2 i hh2 j)
which give
^ 2y ^ 3y = jh2 ; h3 i hv2 ; v3 j + jv2 ; h3 i hh2 ; v3 j + jh2 ; v3 i hv2 ; h3 j jv2 ; v3 i hh2 ; h3 j

^ 3y ^ 2y = jh3 ; h2 i hv3 ; v2 j + jv3 ; h2 i hh3 ; v2 j + jh3 ; v2 i hv3 ; h2 j jv3 ; v2 i hh3 ; h2 j
) ^ 2y ^ 3y = ^ 3y ^ 2y
From part (b) in example 1, we have
2 2
^23 = jc1 j jh2 ; v3 i hh2 ; v3 j+c2 c1 jv2 ; h3 i hh2 ; v3 j+c1 c2 jh2 ; v3 i hv2 ; h3 j+jc2 j jv2 ; h3 i hv2 ; h3 j :
2 2
) ^23 = jc1 j jh2 ; v3 i hh2 ; v3 j+c2 c1 jh2 ; v3 i hv2 ; h3 j+c1 c2 jv2 ; h3 i hh2 ; v3 j+jc2 j jv2 ; h3 i hv2 ; h3 j :

2
^23 ^ 2y ^ 3y = jc1 j jh2 ; v3 i hh2 ; v3 j + c2 c1 jv2 ; h3 i hh2 ; v3 j
2
+c1 c2 jh2 ; v3 i hv2 ; h3 j + jc2 j jv2 ; h3 i hv2 ; h3 j
( jh2 ; h3 i hv2 ; v3 j + jv2 ; h3 i hh2 ; v3 j + jh2 ; v3 i hv2 ; h3 j jv2 ; v3 i hh2 ; h3 j)
Taking into consideration the orthonormality conditions we can simplify
the above expression
2
^23 ^ 2y ^ 3y = jc1 j jh2 ; v3 i hv2 ; h3 j + c2 c1 jv2 ; h3 i hv2 ; h3 j
2
+ c1 c2 jh2 ; v3 i hh2 ; v3 j + jc2 j jv2 ; h3 i hh2 ; v3 j :
Similarily using the results for ^23 and ^ 3y ^ 2y , we have
2
^23 ^ 3y ^ 2y = jc1 j jh2 ; v3 i hh2 ; v3 j + c2 c1 jh2 ; v3 i hv2 ; h3 j
2
+c1 c2 jv2 ; h3 i hh2 ; v3 j + jc2 j jv2 ; h3 i hv2 ; h3 j ( jh3 ; h2 i hv3 ; v2 j + jv3 ; h2 i hh3 ; v2 j
+ jh3 ; v2 i hv3 ; h2 j jv3 ; v2 i hh3 ; h2 j)
2
) ^23 ^ 3y ^ 2y = jc1 j jh2 ; v3 i hh3 ; v2 j + c1 c2 jh2 ; v3 i hv3 ; h2 j + c1 c2 jv2 ; h3 i hh3 ; v2 j
2
+ jc2 j jv2 ; h3 i hv3 ; h2 j
Therefore
~ = ^23 (^ 2y ^ 3y )^23 (^ 3y ^ 2y ):
n
2
~= jc1 j (c1 c2 ) jh2 ; v3 i hh3 ; v2 j + c22 c12 jv2 ; h3 i hh3 ; v2 j
2 2 2
+ jc1 j jc2 j jh2 ; v3 i hv3 ; h2 j + jc2 j (c2 c1 ) jv2 ; h3 i hv3 ; h2 j
2 2 2
+ jc1 j (c1 c2 ) jh2 ; v3 i hh3 ; v2 j + jc2 j jc1 j jv2 ; h3 i hh3 ; v2 j
+c21 c22 jh2 ; v3 i hv3 ; h2 j + c22 (c1 c2 ) jv2 ; h3 i hv3 ; h2 j :
We now determine the elements of the matrix
~ (17.89)
2 3
hv2 ; v3 j ~ jv2 ; v3 i hv2 ; v3 j ~ jh2 ; v3 i hv2 ; v3 j ~ jv2 ; h3 i hv2 ; v3 j ~ jh2 ; h3 i
6 hh2 ; v3 j ~ jv2 ; v3 i hh2 ; v3 j ~ jh2 ; v3 i hh2 ; v3 j ~ jv2 ; h3 i hh2 ; v3 j ~ jh2 ; h3 i 7
=6
4 hv2 ; h3 j ~ jv2 ; v3 i
7
hv2 ; h3 j ~ jh2 ; v3 i hv2 ; h3 j ~ jv2 ; h3 i hv2 ; h3 j ~ jh2 ; h3 i 5
hh2 ; h3 j ~ jv2 ; v3 i hh2 ; h3 j ~ jh2 ; v3 i hh2 ; h3 j ~ jv2 ; h3 i hh2 ; h3 j ~ jh2 ; h3 i
(17.90)
Therefore the matrix can be expressed as
2 3
0 h 0 i 0 0
6 2 2 2 7
6 0 jc1 j jc2 j + c21 c22 jc1 j [c1 c2 + c1 c2 ] 0 7
~=6 6 2
h
2 2
i 7
7 (17.91)
4 0 jc2 j [c2 c1 + c1 c2 ] jc1 j jc2 j + c22 c12 0 5
0 0 0 0
(c) We use mathematica to determine the eigenvalues of the above matrix
(d) The Concurrence: for the case of discrete bipartite density matrix 23 ;
the concurrence, C; is given by
C = max f0; 1 2 3 4g ; (17.92)
in which the 0
ks (with 1 = 2 = 3 = 4) are the square roots of the
eigenvalues of the Hermitian matrix

~ = ^23 ^ 2y ^ 3y ^23 ^ 3y ^ 2y : (17.93)
Using the eigenvalues we determined in part c we have
s
q
1 2 + 4D 2
1 = D 22 + D33 + D22 23 + D32 2D22 D33 + D33
2
s
q
1 2 + 4D 2
2 = D22 + D33 D22 23 + D32 2D22 D33 + D33
2
3 = 0; 4 =0
so that the concurrence can be expressed as
C= 1 2 (17.94)
Analyze the degree of the entanglement applying your result for the con-
currence in part c (i.e. plot E vs. using Mathematica). Make sure that
the result agrees with what you obtained in part e.
Comparing this result with what we obatined using the Von Neumann
entropy (the graph below), we see that the results are identical.
17.9 Quantum analyses of teleportation …delity

The faithful transmission of quantum teleportation is determined by the Fidelity.
The Fidelity in quantum teleportation is given by
F = T r [~1 ~3 ]
where ~3 is the matrix of the density operator ^3 which is the density operator
of the photon where the information is encrypted on. It is given by
^3 = j 3i h 3j
~1 is the matrix element of the density operator ^1 which is the density operator
constructed from the state of the EPR pair that Bob shared with Alice after
she conducted the measurement in her station. When the Fidelity F = 1, we
have perfect faithful transmission of information.
Ex. 3 We recall from our discussion of quantum teleportation that Alice en-
crypted the information that she wanted to deliver to Bob in single quibit
state
j 3 i = c0 j0i + c1 j1i : (17.95)
After she send the EPR pair that she shared with Bob and this single
qubit through a CNOT and H gates, she conducted a measurement. The
17.9. QUANTUM ANALYSES OF TELEPORTATION FIDELITY 423
measurement would result in any one of the following state for the EPR
pair entity that Bob shared with her
8 9
> Measured outcome
>
>
Bob’s qubit >
>
>
>
< j00i h00 j 123 i = 12 (c0 j0i + c1 j1i) >
=
j10i h10 j 123 i = 12 (c0 j1i + c1 j0i) (17.96)
>
> >
>
> j01i h01 j 123 i = 12 (c0 j0i c1 j1i) > >
>
: ;
j11i h11 j 123 i = 12 (c0 j1i c1 j0i)
Show that for a Faithful transmission of the qubit, the Fidelity must be
one.
Sol: For quibit that need to be teleported that density matrix is given by
2
h0 j 3i h 3j 0i h0 j 3i h 3j 1i jh0 j 3 ij h0 j 3 i h 3 j 1i
~3 = = 2
h1 j 3 i h 3 j 0i h1 j 3 i h 3 1i
j h1 j 3 i h 3 j 0i jh1 j 3 ij
(17.97)
Using
j 3i = c0 j0i + c1 j1i (17.98)
we may write
2
jc0 j c0 c1
~3 = 2 (17.99)
c1 c0 jc1 j
For the any one of the outcome of the measurement we have
j 1i = c00 j0i + c01 j1i : (17.100)
with
2 2
jc00 j + jc01 j = 1
Then the density Matrix for ~1 , we …nd
2
h0 j 1i h 1j 0i h0 j 1i h 1j 1i jh0 j 1 ij h0 j 1 i h 1 j 1i
~1 = = 2
h1 j 1 i h 1 j 0i h1 j 1 i h 1 j 1i h1 j 1 i h 1 j 0i jh1 j 1 ij
(17.101)
2
jc01 j c01 c00
~1 = 2 : (17.102)
c00 c10 jc00 j
Then the Fidelity for the Teleportation
F = T r [~1 ~3 ]
becomes
2 2
jc00 j c00 c10 jc0 j c0 c1 2 2 2 2
F = Tr 2 2 = jc00 j jc0 j +c00 c0 c1 c10 +c00 c0 c1 c01 +jc01 j jc1 j
c01 c00 jc01 j c1 c0 jc1 j
(17.103)
For Faithful transmission of the qubit state, Bob by performing a Unitary
transformation on the qubit state
j 1i = c00 j0i + c01 j1i : (17.104)
must be able to reproduce the original state using the outcome of the mea-
surement made by Alice that he received through the classical Channel.
That means for Faithful transmission we must have
c00 = c0 ; c01 = c1 ;
and the Fidelity becomes

2
4 2 2 4 2 2
F = jc0 j + 2 jc0 j jc1 j + jc1 j = jc0 j + jc1 j =1 (17.105)
17.10 Quantum Theory of a photon beam split-

ter
A photon beam splitter has two input port where two beam of light can enter
and two output port where the two input beam can exit out. The beam of light
17.10. QUANTUM THEORY OF A PHOTON BEAM SPLITTER 425
that is incident on each port can be transmitted or/and re‡ected. Suppose the
re‡ection and transmission coe¢ cient for port one is R1 , and T1 , respectively.
Similarly for port two we have R2 , and T2 : Suppose the …rst input port is
described by the basis vector jai and the second port by jbi : Similarly the exit
port 3 by jAi and exit port 4 by jBi : The operation that takes place in the BS
is described by a Unitary operator, U^
From the …gure shown above we can write

jAi ^ jai
jBi = U jbi (17.106)
Using the re‡ection and transmission coe¢ cients for the two ports of the BS we
may write
jAi = R1 jai + T2 jbi ; jBi = R2 jbi + T1 jai (17.107)
Using the Matrix representation, we may write in the jai and jbi basis
A a
=U (17.108)
B b
where
R1 T2
U= (17.109)
T1 R2
is the beam splitter matrix. Since the operation that takes place must be Uni-
tary, we require
U y = U 1: (17.110)
Noting that
T
R1 T2 R1 T1
Uy = = (17.111)
T1 R2 T2 R2
and from Theoretical physics I we recall
T
1 [cof (U )]
U = (17.112)
det jU j
so that using the cofactor matrix is given by
R2 T1
cof (U ) = (17.113)
T2 R1
and
det jU j = R1 R2 T1 T2 = ei (17.114)
where we used the property of a unitary matrix in which the determinant has a
miniguide of one. Thus we may may write
T
1 i R2 T1 i R2 T2
U =e =e (17.115)
T2 R1 T1 R1
If we chose this phase = 0 since it multiples each term, we …nd
R1 T1 R2 T2
Uy = U 1
) = (17.116)
T2 R2 T1 R1
which leads to
R2 = R1 ; T2 = T1 : (17.117)
Using Euler notation
R2 = jR2 j ei r2
; R1 = jR1 j ei r1
; T1 = jT1 j ei t1
; T2 = jT2 j ei t2
(17.118)
we may write
T2 T1
=
R2 R1
as
jT2 j ei t2
jT1 j e i t1
jT2 j i( ) = jT1 j ei( r1 + ):
= ) e t2 r2 t1
(17.119)
jR2 j ei r2
jR1 j e i r1 jR2 j jR1 j
where we used
i
1=e (17.120)
From Eq. (17.119) follows that
jT2 j = jT1 j ; jR2 j = jR1 j (17.121)

t2 r2 = r1 + t1 ) t2 r2 + t1 r1 = (17.122)
This was shown by Zeilinger [ Zeilinger, “General properties of lossless beam

splitters in interferometry,”Am. J. Phys. 49, 882–883 ~1981!. This arti-
cle expresses the general 232 unitary matrix in terms of Pauli spin matrices.
This approach would be particularly useful for further familiarizing students in
a quantum mechanics course with these important mathematical tools.]
Symmetric beam splitter : For a symmetric beam splitter both port 1 and
port 2 have exactly same e¤ect on incident photon. This means it is not only
17.11. A PHYSICAL SCHEME FOR QUANTUM TELEPORTATION 427
the corresponding re‡ection and transmission coe¢ cient magnitudes of the two
port must be exactly the same,
T1 = T2 = T ) jT1 j ei t1
= jT2 j ei t2
= jT j ei t
) t1 = t2 = t (17.123)
and
R1 = R2 = R ) jR1 j ei r1
= jR2 j ei r2
= jRj ei r
) r1 = r2 = r (17.124)
Using these conditions in Eq. (17.122), for a symmetric beam splitter we …nd
t2 r2 + t1 r1 = ) t r = (17.125)
2
If we set the phase for re‡ected beam to zero, we have
r = t = ) R = jRj ; T = jT j ei =2
= i jT j (17.126)
2
and the beam splitter matrix in Eq. (17.109) becomes
jRj i jT j
U= (17.127)
i jT j jRj
where
2 2
jRj + jT j = 1:
For a 50/50 beam splitter
1
jRj = jT j ) jRj = jT j = p (17.128)
2
and the beam splitter matrix becomes
1 1 i
U=p : (17.129)
2 i 1
17.11 A physical scheme for Quantum telepor-

tation
In this section we shall get introduced to a physical scheme that uses the EPR
photon pairs. These EPR pairs can be generated using spontaneous parametric
down conversion (SPDC).
Alice and Bob share two EPR pairs. The photons are polarization entangled
and are described by the ket vector
1
j i23 = p [jh2 ; v3 i + jv2 ; h3 i] (17.130)
2
Alice is interested in teleporting an information encrypted on a qubit state
1
j i1 = p [jh1 i + jv1 i]
2
Figure 17.7: Physical Scheme for quantum Teleportation
Then the state describing the three photons (1-3) can be expressed as that
1 1
j i123 = p [jh1 i + jv1 i] p [jh2 ; v3 i + jv2 ; h3 i] (17.131)
2 2
As shown in Fig. 1 Alice interfere photon 1 and photon 3 using a 50/50 beam
splitter one (BS1 ). From our discussion of the quantum description of BS in
the previous section this operation is described by a unitary operator U ^ , Eq.
(17.129). Then the state of the three photons at the Alice station can be written
as
^j i
j i123 = U (17.132)
123
The teleportation process would be complete when Alice make a measurement
on the two photons and send the outcome of her measurement to Bob through
a classical channel so that Bob would be able to decode the information en-
crypted after he made a similar measurement at his station. Now suppose the
set of detectors (D1 ; D2 ) detect the two photons. We may represent this by the
eigenstate jD1 i jD2 i ; then the measurement action can be described by the
projection operator
^ (D1 ; D2 ) = jD1 i hD1 j jD2 i hD2 j = jD1 ; D2 i hD1 ; D2 j :
Then the collapsed state (after the measurement) would be
^j i
j i3 = hD1 ; D2 j U (17.133)
123
Note that due to the polarizing beam splitter D1 detects only horizontally po-
larized photon which could be photon 1 or 2 and D2 detects only vertically
17.11. A PHYSICAL SCHEME FOR QUANTUM TELEPORTATION 429
polarized photon which could also be either photon 1 or 2. Therefore the de-
tection by the two detectors can result in jh1 ; v2 i or jh2 ; v1 i : Thus we may
write
1
jD1 ; D2 i = p [jh1 ; v2 i + jh2 ; v1 i] (17.134)
2
p
where the factor 1= 2 is due to normalization condition. Then the collapsed
state
1 ^j i 1 h ^ + hh2 ; v1 j U
i
^ j i
j i3 = p [hh1 ; v2 j + hh2 ; v1 j] U 123 = p hh 1 ; v2 j U 123
2 2
(17.135)
Using the matrix representation for symmetric 50/50 beam splitter
1 1 i
U=p : (17.136)
2 i 1
we may write
1 1 i h1 + iv2 ih1 + v2
hh1 ; v2 j U ! (h1 ; v2 ) p = p ; p
2 i 1 2 2
1 1 1
hh1 ; v2 j U = p (hh1 j + i hv2 j ; i hh1 j + hv2 j) = p (hh1 j + i hv2 j) p (i hh1 j + hv2 j) :
2 2 2
(17.137)
Similarly, we can show that

1 1
hh2 ; v1 j U = p (hh2 j + i hv1 j) p (i hh2 j + hv1 j) : (17.138)
2 2
Then the collapsed state after the measurement at Alice station given in Eq.
(17.135) can be expressed using Eqs. (17.137) and (17.138) as
1 1 1
j i3 = p p (hh2 j + i hv1 j) p (i hh2 j + hv1 j) j i123 (17.139)
2 2 2
and substituting Eq. (17.131), we may write
1 1 1 1 1
j i3 = p p (hh2 j + i hv1 j) p (i hh2 j + hv1 j) p [jh1 i + jv1 i] p [jh2 ; v3 i + jv2 ; h3 i]
2 2 2 2 2
(17.140)

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Quantum Mechanics I & II Lecture Note

February 26, 2019

I Quantum Mechanics I-PHYS 4380 1

3 Rotation of Basis States and Matrix Mechanics 51

5 Time evolution of a quantum system 123

6 Interacting two spin-1/2 particles 143

7 Wave mechanics in one dimension 157

8 Classic 1-D quantum problems 187

9 The Harmonic oscillator 223

10 Orbital angular momentum and hydrogenic atoms 243

II Quantum Mechanics II -PHYS 4390 261

11.2 PT application I - The Stark e¤ ect . . . . . . . . . . . . . . . . . 276

12 Many-particle systems 317

13 Quantum …eld theory 345

14 Quantum description of charge-…eld interaction 367

16 Introduction to relativistic quantum mechanics 381

16.3 Relativistic wave equation for spin-1/2 particles-the Dirac-equation 391

17 Intro to quantum informatics 393

Review of relevant topics

1.1 Vectors and Dirac notation

~ is the complex conjugate of A:

and if the vectors are orthogonal,

Orthonormal set of vectors: We recall the Cartesian unit vectors, x

and have unit magnitude

Suppose, using Dirac-notation, if we represent these unit vectors as

The Cartesian unit vectors satisfy the orthonormality condition

hej jei i = ij (1.8)

where ij is the Kronecker delta

haj jai i = ij (1.10)

are known as an orthonormal set of vectors.

hA jAi = (he1 j A1 + he2 j A2 + he3 j A3 ) (A1 je1 i + A2 je2 i + A3 je3 i)

Furthermore we note that the components of the vector can be determined as

he1 jAi = A1 he1 je1 i + A2 he1 je2 i + A3 he1 je3 i = A1 ;

fA1 (x) ; A2 (x) ; A3 (x) :::An (x) :::g (1.17)

that meet the requirement

where C is a constant, are said to form an orthogonal set of functions. Using

hAn (x) jAm (x)i = Cn nm (1.20)

so that the for the set of functions de…ned by

one can write

These set of functions are said to form an orthonormal set of functions.

Example 1.1 Show that the set of functions de…ned by

for n = 1; 2; 3::::form an orthonormal set of functions for all x ( ; ).

Solution: Using Euler’s formula, we can express

1.2 Orthogonal matrices, the rotational opera-

Figure 1.1: A counter-clockwise rotation of the Cartesian coordinate about z-

Figure 1.2: Coordinate rotation using Dirac formulation.

where we used matrix representation.

1.3 Eigenvalues and Eigenvectors

Under this transformation if the vector ~r0 is expressible as

one can put Eq. (1.41)

The eigenvalues are obtained from the condition

The eigenvector for 1 can then be written as a column matrix

Eigenvalue equation for Hermitian Matrices: A Hermitian Matrix is a matrix

The Similarity Transformation: The similarity transformation of the matrix

1.4 State vector, average, and standard devia-

Figure 1.3: Two sides of a penny represented using bra-vectors.

and the corresponding bra vector h j

Then the bra-ket of "the sate vector of the coin" becomes

Substituting the relation

one can write the average value as

For the coin toss game, this becomes

the standard deviation becomes

We recall that A is the average value which is independent of the summation