Chapter 3

Formalism of Quantum Mechanics

3.1 Quantum Systems
In this course, only non-relativistic quantum mechanics is considered. Clearly, the case of photons is excluded since cases. 1. A single structureless particle moving in a force eld. The source of the force eld is not included in the system. 2. A collection of structureless particles (identical or otherwise, distinguishable or otherwise) interacting with each other and a force eld. 3. A collection of the particles with internal degrees of freedom (like spin) where there is no classical discription. Classical mechanics treats the rst two cases. In these cases, the description of the quantum system is based on the classical description. The third case will be handled separately, later.

E = pc.

Thus, by quantum system, one means one of the following

3.2 Postulates of Quantum Mechanics

Before the working postulates of the quantum mechanics are presented, note the following:

The mathematical rigour is not followed strictly, thus making the postulates incomplete. However, in introductory course, these are enough. The aim is to present a operational quantum mechanics for describing observed world.

The following table gives the postulates as compared to those of classical mechanics given for a case of a single particle in external force eld in 1D. Generalization to 3D or many particles is immediate.

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I II

Classical Mechanics A state of a classical system is given by a pair of real numbers (x, p), with x being position and p being momentum of the particle. An observable or a dynamical variable is a real valued function of x and p, denoted by (x, p).

Quantum Mechanics A state of the quantum system is given by a vector in some Hilbert space H.
and P be two operators on H, Let X such that P =i . X, is is called position operator and P called momentum operator. An observable is represented by a hermitian operator X = x X, pP

III

A measurement of an observable is (x, p). The act of measurement does not disturb the state of the system.

obtained by substituting the operators in place of x and p in classical expression. A measurement of an observable yields . a value from the set of eigenvalues of with If is an eigenvector of eigenvalue , then the probability of obtaining as a result of measurement on system in state is given by
P () | , |2 .

IV

The time evolution of the state is given by Newton's laws.

d p x(t) = dt m d p(t) = F (x, p, t) dt

As a result of measurement the state of the system suddenly changes from to . The time evolution of the state of the system is given by Schrdinger equation:
i d (t). (t) = H dt is the operator corresponding Where H to the classical Hamiltonian of the system.

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Discussion

The rst three postulates are about the state of the system and computing the value of the measurement of dynamical variables at some instant. Postulate I denes the state of the system. To begin with, the choice of the Hilbert space is arbitrary. Any Hilbert space will do! In the table given below, the most common choice is given. Note that since is an element of a Hilbert space, superposition principle is automatic. Postulate II is a correspondance between the classical dynamical variables with the operators on H. Again, choice of position operator and momentum operator is arbitrary, except the commutator relationship between the two. The postulate is fuzzy on the issue of order of operation, that is, it is unclear whether the P or P X or X P +P X /2. The last choice is appealing classical variable xp will be X since the operator is hermitian. Postulate III contains lot of information. One can organize this information in following steps:
, nd all eigenvalues (must be real since is hermitian). Suppose the 1. Given set of eigenvalues is discrete and is given by = {i | i = 1, 2, . . .}. Let B = {i | i = 1, 2, . . .} be the set of corresponding eigenvectors. B is an orthonormal basis of H. 2. Now expand the state of the system in terms of i , =
i

Ci i

where Ci = i , . 3. The sample space of measurement of is . Probability of getting i as a result of measurement is given by
P (i ) = | i , |2 . are continuous, procedure is still the same: If the eigenvalues of , nd all eigenvalues (must be real since is hermitian). In this case, the 1. Given set of eigenvalues is some subset of R say, R. Let B = { | } be the set of corresponding eigenvectors. B is an orthonormal basis of H. 2. Now expand the state of the system in terms of i , =

C ( ) d

where C () =

. 19

3. The sample space of measurement of is . Probability density function for getting as a result of measurement is given by

P ( ) = | , |2 . One can dene a projection operator as follows: Let B = {i | i = 1, 2, . . .} be an orthonormal basis of H. Then any state can be expanded in terms of i , =
i

Ci i

where Ci = i , . Let Pi be an operator such that

Pi = i , i .
Note this projection operator has the same geometric interpretation as that of projection on coordinate axes in plane geometry. Clearly,

=
i

Pi =
i

Pi = I

where I is the identity operator.

Note that the Postulate III also mentions that a measurement will abruptly change the state of the system. Suppose measurement is done and yields a result i . Then the new state will be i . This is called as the collapse of the wavevector. The probabilities given in Postulate III are to be interpreted in frequency or ensemble sense (See Math Primer.).

3.3 Wave Mechanics

In chapter 2, the QM was introduced using wavefunctions. That is a free particle was associated with a wavefunction (x, t), and probability density function of its location with |(x, t)|2 . When the Hilbert space is chosen to be L2 (R), the quantum mechnics is more popularly known as wave mechanics.

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I II

Quantum Mechanics A state of the quantum system is given by a vector in some Hilbert space H.
and P be two operators on H, Let X such that P =i . X, is is called position operator and P called momentum operator. An observable is represented by a hermitian operator X = x X, pP

Wave Mechanics Let H = L2(R). The state of the system is given by a square integrable function (x). and P Choose X
(x) = xf (x) Xf f (x) = i d f (x). P dx

Check that
P =i X,

III

obtained by substituting the operators in place of x and p in classical expression. A measurement of an observable yields . a value from the set of eigenvalues of If is an eigenvector of with eigenvalue , then the probability of obtaining as a result of measurement on system in state is given by
P () | , |2 .

holds.

IV

As a result of measurement the state of the system suddenly changes from to . The time evolution of the state of the Classical Hamiltonian in case of system is given by Schrdinger equation: conservative force eld is just the total energy, that is d
i dt (t). (t) = H is the operator corresponding Where H to the classical Hamiltonian of the system. P2 + V (x) 2m 2 d2 X = +V H 2m dx2 H =

The Schrdinger equation becomes

i
2 d2 (x, t)+V (x)(x, t). (x, t) = t 2m dx2

Here are some features of wave mechanics: 21

The choice of the position operator and momentum operator are not unique. Here is an alternate choice:
(p) = i d f (p) Xf dp f (p) = pf (p). P P = i holds. This assignment is called momenThis choice is as good since X, tum space representation as opposite to the earlier choice, which is called real space representation.(The choice of p as a dummy variable is only due to its popularity.) on L2 (R) are continuous. The set of eigenvalues is just = R! The eigenvalues of X X . The eigenvector corresponding to That is every real number is an eigenvalue of X an eigenvalue is (x) = (x ). Thus the set of eigenvectors is BX = { | R} .

Check:
 BX  BX

is orthonormal, that is
, = ( ).

is complete, that is every function can be written as

f (x) =
R

f () (x )d =

f () (x)d

Probability density function for nding particle at as a result of measurement on a system which is in state at an instant t , is given by
2 PX (, t) = | , | = (x )(x, t)dx 2

= |(, t)|2

Now, what are the eigenvalues and eigenvectors of the momentum operator on L2 (R)? Again P = R. For any real number p, let p (x) = exp (ipx/ ) / 2 . Now
p (x) = P i d dx 1 exp 2 ipx = pp (x)

Thus, the set of eigenvectors are

BP = {p (x) | p R} .

Again Check: 22

 BP

is orthonormal, that is

p , p
(See tutorial problem 1.4)

= (p p ).

 BP

is complete.

Remember, every square integrable function admits a fourier

transform, that is every function can be written as

f (x) =

1 g (p) exp 2 = g (p)p (x)dp

R

ipx

dp

Probability density function for the particle to have momentum surement on a system which is in state

as a result of mea-

at an instant

, is given by

2 PP (p) = | p , | 1 ipx = exp 2 = |(F ) (p)|2

Where

(x)dx

is the fourier transform of

This formula is identical to the one given in

case of a free particle in previous chapter.

Neither the eigenfunctions of

nor the eigenfunctions of

belong to

these are orthonormal set of functions that span worrying about mathematical diculty.

L2 (R),

L2 (R).

However,

thus these will be used without

3.4 Schrdinger Equation

In classical mechanics, if a single particle is moving in a conservative force eld then the total energy is a constant of motion. In most parts of this course, only conservative force elds are considered. The hamiltonian function (that is total energy) is then independent of time. Assume, that the hamiltonian operator there is no explicit dependence on

on hilbert space

is independent of time (that is

t).

Let the set of eigenvalues of

be given by

H = {E1 , E2 , . . .}
with correpsonding set of eigenvectors

BH = {1 , 2 , . . .}.
That is, for each

i,

i = Ei i . H
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This equation is called time independent Schrodinger equation. And the eigenvectors i are stationary states. The eigenvalues Ei are called energy eigenvalues. The set is called the H energy spectrum. Remeber BH is an orthonormal basis of H. Let (t) be the state of the system at some time t. Then,
(t) = ci (t)i

Putting this in Schrodinger equation we get

i
i

d ci (t) i = dt d ci (t) i = dt

i ci (t)H
i

(Ei ci (t)) i
i

Equating the coecients on either side

i d ci (t) = Ei ci (t) dt

Solving this dierential equation,

ci (t) = ci (0)eiEi t/

Thus1
(t) = = e ci (0)eiEi t/ i
i iHt/ i

ci (0)i = eiHt/ (0)

(t) = exp iHt/ The operator U is called as time evolution operator. Check Now, if t = 0, the state of the system is one of the stationary states, say (t = 0) = i for some i, the time evolution of the state of the system is given (t) = eiEi t/ (0)
1

For given operator A, dene

exp [A] = 1 + A + 1 2 1 A + + An + 2! n!

If the series on rhs converges, eA is a well dened operator. Now, check by brute force method, that if Au = u then
eA u = e u

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Now consider an observable with eigenvectors with eigenvalue . The probability that measurement of will yield , at a time t is
P (, t) = | , (t) |2 = eiEi t/ , (0) = | , (0) |2 = P (, 0)
2

Thus, if system is in a stationary state then all properties of the system are independent of time.
3.5 Uncertainty Principle

state (normalized) , then the average (expectation) value of , denoted by

Expectation Value . If the quantum system is in Theorem 6. An observable is represented by an operator

, is given by

= , .

be = {i | i = 1, 2, . . .}. Let B = {i | i = 1, 2, . . .} be the Proof. Let the spectrum of set of corresponding normalized eigenvectors. Let =
i

Ci i

where Ci =

i ,

. If is normalized. Then
, =
i j

Ci Cj i , j Ci Cj i,j =
i j i

1 =

|Ci |2 .

By postulate III, the probability of getting i as a result of measurement is given by

P (i ) = | i , |2 = |Ci |2

if is normalized. Clearly
i

P (i ) = 1.

The expectation value of the observable is then

=
i

i P (i ) =
i

i |Ci |2

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Now,
, =
i j

j Ci Cj i , Ci Cj j i,j
i j

= =
i

i |Ci |2

Denition 7. The uncertainty in the measurement of an observable in a system that is in

state is dened as
=
2

Theorem 8. If A and B are two observables of a system which is in state , then

(A) (B )
Proof.
2 2

1 2i

B A,

A and g = B B . (Note the subscript in Let f = A has been dropped for brevity.) Now (A)2 = f, f and (B )2 = g, g . Then by Schrwarz inequality, (A)2 (B )2 = f, f g, g | f, g |2

And,
f, g = = A A B A A B , B B . B

Simillarly, Now for any complex number z

A A g, f = B

|z |2 = (Re z )2 + (Im z )2 (Im z )2 =

1 (z z ) 2i

Now let z =

f, g

. Then
| f, g |2 = 1 ( f, g g, f ) 2i 1 2i B B A A
2 2

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Putting everything together

(A)2 (B )2 1 2i B A,
2

and P , then Apply this to X (X )2 (P )2 = 1 2i

2

P X, .

This is Heisenberg's Uncertainty Principle. Minimal Interpretation of the uncertainty principle is ensemble interpretation. That is, a large number of copies of the system are made and set in state . Make measurement of X on half of them. Make measurement of P on the other half. Now from the samples compute uncertainties, that is standard deviation X and P . Uncertainty principle says that
X P 2 .

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