Documente Academic
Documente Profesional
Documente Cultură
Introduction
So far we have seen that a wave like characteristic could be associated with a material
particle like electron, proton, neutron, atoms etc. In 1926, Erwin Schrodinger developed an
equation for the wave associated with these elementary (small mass) particles which would
describe the behaviour of the particles. The solution of the wave equation should describe the
particle aspect, wave aspect and should also be consistent with the uncertainty principle.
Wave function
The quantity that characterises the de-Broglie wave is called the wave function. It is usually
r
r
denoted by (r , t) . It is a function of space, variables r ( x, y, z ) and time t. This gives complete
information about the state of a physical system at a particular time. It is also called the
state function and represents the probability amplitude. lf is large the probability of
finding the particle is also large. lf is small then the probability of finding the particle is
small. The wave function gives the likelihood of finding the particle at a given instant and at a
given position.
Physical significance of wave function
As explained earlier, the wave function signifies the probability of finding the particle
described by the wave function at the point (x, y, z) and at time t. The wave function has the
following three basic properties.
(i) It can interfere with itself (phenomenon of electron diffraction)
(ii) lt is large in magnitude where the particle (electron) or photon is likely to be
located and small at other places.
(iii)The wave function describes the behaviour of a single particle or photon and
not the statistical distribution of a number of such quanta.
Probability density
2
The probability of finding a particle described by the wave function is proportional to i.e.,
the square of the magnitude of the wave function (amplitude). We say
is the probability
,
,
must also be continuous.
x y z
2
, the propagation constant. The equation of the wave
y = A e -i (t - kx)
The energy of the wave is E = h , according to the quantum theory and hence
E
h
= 2 =
k=
2 E
E
=
h
h
h
1 px
or
and
h
p
2 2
px x
h
h
y = A e-i (t - kx)
=Ae
=Ae
Et p x
-i
x
h h
-
i
Et - p x x
h
If is the wave function associated with a particle then the equation can be given by
(x,y) = A e
=Ae
i
Et - p x x
h
i
px x - Et
h
Differentiating w.r.t. t,
i
p x x - Et -iE
h
=Ae
h
t
-i
=
E
h
Or
E -
h
i t
h
=Ae
h
x
i
p x x - Et i 2 p 2x
2
h
=Ae
2
x 2
h
And
p 2x
= - 2
h
2
2
2
p
x = - h
x 2
For a particle of mass m, moving with a velocity v; the total energy of the particle is given by
E = KE + PE = T + V
E=
p 2x
+v
2m
E =
p 2x
+v
2m
h
h2 2
=+v
i t
2m x 2
ih
h2 2
=+v
t
2m x 2
ih
h2 2
=+ v
t
2m
h2 2
ih
=
t
2m
2. For a given system when we solve the Schrodingers equation, substituting the proper
value of potential
energy, we get the solutions of the differential equation which are called Eigen
functions. The corresponding energy values are called Eigen b values.
3.
h2 2
(x,y) = A e
Differentiating w.r.t. t we get,
i
Et - p x x
h
i
p x x - Et -iE
h
=Ae
h
t
-i
=
E
h
h2 2
ih
=+v
t
2m x 2
ih
-i
h2 2
E = +v
h
2m x 2
E = -
h2 2
+v
2m x 2
2
m 2 2
m
=+ 2 v
2
2
h
x
h
2 2m
+ 2 E - V
x 2
h
This is Schrodingers time independent wave equation. The wave function is a function
of only one variable x. Extending this to three-dimensions,
2 +
2m
E - V
h2
Note:
1. Schrodingers wave equation is not valid for relativistic particles since in deriving the
equation the classical expression for energy and momentum are used namely
E=
p2
+ V and p = mv.
2m
1
mv 2 which is also a non-relativistic expression.
2
= A 2 cos 2 t
t
2
= - A (2 ) 2 sin 2 t
2
t
= - 4 2 2
=-
4 2 v 2
2
4 2 m 2 v 2
+
=0
x 2
h2
The total energy of the particle is given by,
E = kinetic energy + potential energy
E=
1
mv 2 + v
2
mv 2 = 2 (E - V)
m 2 v 2 = 2m (E - V)
2
8 2 m
+
(E - V) = 0
x 2
h2
2
2m
+ 2 (E - V) = 0
2
x
h
Extending this to three dimensions, the Schrodingers time independent equation for a nonrelativistic particle
is given by,
2 +
2m
(E - V) = 0
h2
Since this equation is independent of time, it gives the steady state form. It is very useful in
systems when the energy of the particle is very small as compared to the rest energy of the
particle.
Borns interpretation of the wave function
An analogy between the wave function(x, t) and the location of the particle was given by
Born in terms of the relation between intensity of light and the intensity of electron beam.
Consider a beam of light (electromagnetic wave) incident normally on a screen. It is the result
of periodically varying electric and magnetic fields perpendicular to each other and to the
direction of propagation of the wave. The electric field vector is given by, E = A sin (kx t),
where A is the maximum value of the electric field. We know that, the intensity I of an
2
Hence, I = c 0 E = N h
c 0 2
E
h
N E
This however is true only when the intensity of the beam is large i.e., N is large. The
probability of striking of a photon on the screen is large at points where the intensity in the
diffraction pattern is a maximum. In the case of a single photon, the probability of striking the
screen is maximum at points where the wave theory predicts a maximum and lowest at place
where the wave theory predicts a minimum. Thus, E 2 is a measure of the probability of
the photon crossing unit area in unit time at the point under consideration. In one
dimension, E 2 is a measure of the probability per unit length of finding the photon at the
position x at time t.
In a similar way, Max Born interpreted that the square of the amplitude of the wave function
at a point is a measure of probability density (i.e., the probability per unit volume) of the
particle. It is given by P = * , where * is the complex conjugate of . it should be
remembered that is a complex quantity while E is real and observable. Hence, itself has
no physical significance but only 2. Thus the integral of 2 over all space must be equal to 1.
i.e.,
2
8 2 m
+
(E - V) = 0
x 2
h2
This equation is of the form
2
8 2 m
2
2
,
where
+
k
=
0
k
=
E
x 2
h2
The solution is of the form
= A cos kx + B sin kx
where A and B are constants depending on the boundary condition.
At x = 0, = 0
Hence,
0 = A cos 0 + B sin 0
A = 0.
Again at x = L, = 0
Hence
0 = B sin kL
Since B 0, sin kL = 0
8 2 mE
h2
sin
L = 0
8 2 mE
L = n
h2
Where n = 1, 2, 3 ,
8 2 mE 2
L = n 2 2
2
h
n 2 h2
En =
8m L2
This equation gives the Eigen values of energy (proper values). The energy corresponding to
n=1 is called the ground state energy. The other energies are called excited states.
To evaluate B
Consider
8 2 m E
x
h2
= B sin
Since the particle is inside the box, the probability of finding the particle is 1. Hence, using the
normalization condition,
L
dx = 1
sin
sin 2
B2
2
8 2 m E
x dx = 1
h2
n x
dx = 1
L
2sin
0
n x
dx = 1
L
L
B2
n x
1-cos
dx = 1
2 0
L
B2
L
x 0 = 1
2
B2 L
=1
2
B=
2
L
n =
2
n
sin x , where n=1,2,3
L
L
1 =
2
sin x ;
L
L
2 =
2
2
sin
x;
L
L
3 =
2
3
sin x
L
L
These functions are identical with the allowed amplitude functions for the standing waves in a
vibrating string fixed at both ends. The energy levels and the corresponding wave functions
and the probability densities for the first three states are show.
2 +
2m
(E - V) = 0
h2
2 +
2m
E=0
h2
2 2 2
p2
2 2 + 2= 0
2
y
z
h
x
where is E =
p2
,and p is the magnitude of the total momentum of the particle. is a function
2m
px
p
x + Bx sin x x
h
h
p
p
y = A y cos y y + B y sin y y
h
h
pz
pz
z = A z cos
z + Bz sin
z
h
h
x = A x cos
x y z
= A x A y A z sin
= A sin
n
n x
n
x sin y y sin z z
lx
ly
lz
n
n x
n
x sin y y sin z z
lx
ly
lz
where A = Ax Ay Az and nx, ny, nz are independent integers. Since the particle exists inside the
box, the probability of finding the particle inside the box is one.
l x l y lz
dx dy dz = 1
0 0 0
A=
8
=
l x l y lz
8
v
(n x , n y , n z ) =
n
8
n
n
sin x x sin y y sin z z
v
lx
ly
lz
2 h2
E(n x , n y , n z ) =
2m
Note:
n 2x n 2y n 2z
2 + 2 + 2
l x l y l z
1. In one dimensional box we use only one quantum number n while in a three
dimensional box we require, three quantum numbers one corresponding to each coordinate x, y, z.
2. If nx, or ny or nz is zero, = 0. This implies the absence of the particle inside the box.
But this is not physically acceptable. Hence, none of the quantum numbers can be zero.
The ground state corresponds
nx = ny = nz = 1. Hence
(1,1,1) =
E(1,1,1) =
2 h2
2m
1 1 1
2 + 2 + 2
l x l y lz
3. For a single value of energy or momentum there are three different quantum states.
The property of two or more quantum states of a particle having different
sets of quantum numbers and different Eigen functions to have the same
value of momentum and energy is called degeneracy.
V(x) = - F(x) dx
0
= k x dx
0
1
k x2
2
d2 x
= - kx
dt 2
d2x
-k x
=
= - 2 x
2
dt
m
wkt,
k = m (2) 2
= 4 2 m 2
Substituting in equation
1
4 2 m v 2 x 2
2
= 2 2 m v2 x 2
V(x) =
2
2m
+ 2 (E - V) = 0
2
x
h
2
2m
+ 2 (E - 2 2 m v 2 x 2 ) = 0
2
x
h
2m E
h2
2 m
=
h
=
Let
2
2m
+ 2 ( - 2 x 2 ) = 0
2
x
h
y= x
y
=
.
x
y x
2
=
2
x
x x
=
y
y
. =
x y x
y x x
=
y
=
2
y 2
y x
2
+ ( - y 2 ) = 0
2
y
2
+ y 2 = 0
2
y
Hence,
2m E
h2
2 m
(2n + 1)
En
= (2n + 1)
h
E n h (2n + 1)
h
= (2n + 1)
2
En h n +
1
3
5
h , h , h etc. This shows that the
2
2
2
Again, when n = 0, the energy is not zero. This is the zero point energy which is a
consequence of the uncertainty principle.
The Eigen wave functions can be shown to be
n (x) =
Where =
2n n!
1
2
- x 2
2
H n ( x)
mk
and Hn (x) is the Hermite polynomial of the nth order.
h2
The quantised energy levels of the harmonic oscillator are shown in the figure below.
Note:
1. The energy levels for the harmonic oscillator are equally spaced while in the case of
particle in a box
the energy levels diverge.
2. The wave function is given by,
2n n!
n (x) =
1
2
- x 2
2
H n ( x)
0 =
1
4
- x 2
2
The plot of the ground state wave function is shown in figure below
When n=1,
H n (x) = 2 x
1
2
1 =
1 =
1
4
- x 2
2
2 x
x e
- x 2
2
The plot of the first excited state wave function is shown in figure below
h
. The
2
nh
where n, the principal quantum number can
2
degrees 2 of freedom with position coordinates q 1, q2, q3... qn and with momentum coordinates
p1, p2, p3, ..., pn then the phase integral of such a system can be defined as J i =
dq i
According to the quantization rule only those orbits are allowed as stationary states for
which each phase integral is Integral multiple of Plancks constant in a complete
period.
i.e.
dq i = ni h, where ni = 1, 2, 3, etc.
n 2 h2
8m L2
1
2
2 2
n h
where n = 1, 2, 3, etc.
8 2
These expressions for energy clearly indicate that the energy levels in these cases are not
continuous but discrete and quantized. According to classical mechanics the energy can range
from zero to infinity.
Probability
In classical mechanics, the position of an electron is clearly defined. Classically the particle is
equally to be found at any point within the box for a particle in a box but according to
quantum mechanics the probability of finding the particle is maximum at the antinodes and
minimum at the nodes. in quantum mechanics, the probability of finding the particle is given
by the wave function . The probability density is given by || 2 and is a measure of finding
the particle at a particular place at a given time. In classical mechanics the position and
momentum are well defined and can be determined accurately. In quantum mechanics,
according to Heisenberg's uncertainty principle the position and momentum cannot be
simultaneously accurately determined. If x and are the uncertainties in position and
momentum then, x h . The other forms of the uncertainty are in energy and time as
given by E t h and in angular momentum and angular displacement as given by J
h.
Though the calculations involving the measurement of position and momentum of bodies of
large masses are remarkably accurate, the situation is different In the case of small particles
such as electrons. The statements regarding the exact position and velocity of an electron are
replaced by probability. In fact the Bohr concept of an atom in which the electrons revolve
round the nucleus in definite orbits must be abandoned and replaced by a theory which
considers the probability of finding the electron in a particular region of space at a given time.
Dual character
In classical mechanics, matter and energy are considered to be two separate entities having
no relation whatsoever between the two. But we have seen, according to de Broglie a wave
characteristic could be associated with a material particle. The de Broglie wavelength is given
by =
h
, where m is the mass of the particle moving with a velocity v.
mv
WORKED EXAMPLES
1.An electron is constrained in a one dimensional box of side 1 nm. Obtain the first three
eigen values in eV.
Solution: The eigen values of energy are given by,
En =
n 2h2
8m l2
For n=1
1 (6.625 1034 ) 2
E1 =
J
8 (9.111031 ) (109 ) 2
(6.625 1034 ) 2
eV
8 (9.111031 ) (1018 ) 1.6 10 19
= 0.377 eV
The second and third Eigen values of energy are
E2 = 22 X 0.377 = 1.508 eV
and
E3 = 32 X 0.377 = 3.393 eV
2. Find the momentum and energy values for an electron in a box of length 1 for n=1and
n=2.
Solution: Momentum is given by,
pl =
nh
2l
For n=1,
p1 =
h
6.625 1034
=
= 3.313 1024 kg m s 1
10
2l
2 10
For n=2,
p 2 =2
h
6.625 1034
=2
= 6.625 1024 kg m s 1
2l
2 1010
n 2h2
En =
8m l2
For n=1,
E1 =
1 (6.625 1034 ) 2
J
8 (9.111031 ) (1010 ) 2
(6.625 1034 ) 2
=
eV
8 (9.111031 ) (1020 ) 1.6 1019
= 37.61 eV
For n=2,
E2 = 4 X 37.61 eV = 150.44 eV
3. The period of a linear harmonic- oscillator is 1 millisecond. Find its zero point energy in eV.
1
= 103 Hz
T
h
2
eV = 2.07 1011 eV
19
1.6 10
=
4. The energy of a linear harmonic oscillator in its third excited state is 0.1 eV. Calculate its
frequency.
Solution:
En h n +
2
19
0.11.6 10
=
= 6.895 1012 Hz
34
(7 / 2) 6.625 10
5. A proton is confined to a nucleus of radius 10
-14
En =
n 2h2
8m l2
For n=1
E1 =
1 (6.625 1034 ) 2
J
8 (9.111031 ) (1014 ) 2
(6.625 1034 ) 2
eV
8 (9.111031 ) (1028 ) 1.6 10 19
= 2.05 eV
The second and third Eigen values of energy are
E2 = 22 X 2.05 = 8.2eV
and
E3 = 32 X 2.05 = 18.45 eV
6. Calculate the zero point energy and the spacing of the energy levels in a one dimensional
oscillator with an oscillator frequency of 1 kHz.
Solution:
1
h
2
1 6.625 1034 103
=
2 1.6 1019
= 2.073 1012 eV
E0
E0 h n
2
En =
n 2h2
8m l2
1 (6.625 1034 ) 2
E1 =
8 (9.111031 ) (0.2 10 9 ) 2
1511.6 1019
n2 =
n 2 (6.625 1034 ) 2
8 (9.111031 ) (0.2 109 ) 1.6 10 19
n =
n =4
8. Find the probability that a particle in a one dimensional box of length L can be found
between 0.4 L to 0.6 L for the ground state.
Solution: The wave function in one dimensional box of length L for a free particle is given
by
n =
2
nx
sin
L
L
2
nx
sin
.
L
L
2 2 nx
sin
x
L
L
Mean position, x =
2
nx
sin
. x
L
L
0.4 L + 0.6 L
L
= 0.5 L =
2
2
2 2
sin
0.2 L
L
2
= 0.4
Pn x =
EXERCISES
I Questions
1. Obtain the time independent Schrodingers equation. Give its physical significance.
2.
3. Write Schrodingers wave equation tor a free particle. What is the physical
interpretation of the wave function ? Explain Borns interpretation.
4. Explain the terms eigen values and eigen functions. Give the physical significance of a
wave function.
5. Explain the requirements that are imposed on a physically acceptable wave function.
6. Obtain the Schrodingers equation for a particle in a one dimensional box and solve it to
obtain the energy eigen values. Also represent the first three wave functions in a graph.
7. Write down the Schrodingers equation for a particle in a one dimensional box. Show
that the linear momentum and energy of a particle in a one dimensional box is
quantised.
8. Obtain Schrodingers equation for a linear harmonic oscillator. Solve it to obtain the
energy eigen values.
9. Show that the energy of a harmonic oscillator is quantised in steps of h. Explain the
existence of zero point energy.
10.Bring out a comparison between the classical and quantum ideas with reference to the
quantisation of energy and angular momentum.
11.What is the basic difference between the postulates of classical and quantum theory?
II Concept questions
12.Distinguish between a free particle and particle in a box.
13.The zero point energy of a harmonic oscillator is not zero. Explain.
14.A bound particle has quantised energy values whereas it is not so for a completely free
particle. Explain.
15.The concept of trajectory has no significance in quantum mechanics. Explain.
16.Bring out the physical significance. of zero point energy.
17.Explain the concept of Bohrs stationary orbits on the basis of quantum mechanical
model of the atom.