1 Quantum Mechanics

1.1 QUANTUM FREE ELECTRON THEORY

Following de Broglie’s hypothesis of matter waves and Schroedinger’s matter
wave equaion, Sommerfeld proposed the quantum free electron theory. He assumed
that the valence electrons are free in ametal piece and they are moving in an uniform
potential within the metal. He assumed that a moving electron behaves as if it is a
system of waves, called matter waves. By this theory Sommerfeld correctly predicted
the values of specific heat of metals, electrical conductivity and thermal conductivity of
metals.

1.2 DE BROGILE WAVES

A wave is spread out over a relatively large region of space and it cannot be said
to located just here and there. Actually a wave is nothing but rather a spread out
disturbance. A wave is specified by its frequency, wavelength, phase or wave velocity,
amplitude and intensity.
A particle (matter) has mass and it is located at some definite point. It can move
from one place to another and it gives energy when slowed down or stopped. The
particle is specified by its mass, velocity, momentum and energy.
Considering the above facts it appears difficult to accept the conflicting ideas
that radiation has a dual nature. That is, radiation is a wave which is spread out space
and also a particle which is localised at a point in space.
However this acceptance is essential because the experimental results for black
body radiation, photoelectric effect and X-ray absorption are explained by considering
the radiation to appear as a stream of particles.
1.2 ENGINEERING PHYSICS - II

The success of Planck’s interpretation of black body radiation, Einstein’s

interpretation of photoelectric effect, Bohr’s interpretation of the line spectra, Compton’s
interpretation of the scattering of X-rays, etc., convinced everyone of the photon
character of radiant energy. On the other hand, electromagnetic radiation, which includes
visible light, infrared and ultraviolet radiation, X-rays and gamma rays was shown to be
a wave motion by interference and diffraction experiments. Radiation thus exhibits a
dual wave-practicle nature.
One can use either the wave aspect or the particle aspect of light to explain the
above observed phenomena as it suited them. Here it should be remembered that radiation
like light cannot exhibit its particle and wave properties simultaneously.
de Broglie waves or Matter waves: The waves associated with the particles of
matter (e.g. Electrons, protons, etc.,) are known as matter waves or pilot waves or de
Brogile waves.

1.3 de BROGLIE’S HYPOTHESIS

In 1924, Louis de-Broglie made a daring suggestion that like radiations matter
also exhibits dual characteristic. In other words, particles of matter like electrons and
protons also exhibit wave properties. de Broglie’s suggestions were based on the
following facts :
1. The entire universe consists of matter and radiation (energy) only.
2. Nature is symmetrical in so many respects. Therefore the two physical entities
viz matter and energy must be mutually symmetrical. That is to say if radiant
energy has dual characteristic, matter must also have dual (i.e. particle like
and wave like) nature.
So a moving particle is associated with a wave which is known as matter wave
and its wavelength is given by

h h
  
mv p

Where m is the mass of the particle; v is its velocity and p is its momentum.
Derivation of de Broglie equation
The expression of the wavelength associated with a material particle can be
derived on the analogy of radiation as follows :
QUANTUM MECHANICS 1.3

Considering the Planck’s theory of radiation, the energy of a photon is given by

hC
E  hv  ( wave aspect)

Where C is the velocity of light in vacuum and  is its wavelength. If the photon
is considered as particle of mass m then according to Einstein’s mass - energy relation,
the energy of the photon is given by
E = mC2 (particle aspect)
Since the energy of the photon in the two cases is the same, therefore from
equations (A) and (B) we get

hC
 mC 2

hC h
(or)   2

mC mC
The quantity mC = p, the momentum of the photon and therefore

h
 
p

de Broglie carried over this idea to material particles. Thus if a particle has a
mass m and travels with a velocity v, its momentum is mv and the wavelength associ-
ated with this particle is given by

h h
λ= =
mv p
de Broglie’s wavelength associated with electrons
Let us consider the case of an electron of mass m and charge e, accelerated by
a potential V volt from rest to velocity v. Then,
Energy gained by electron = eV

1
Kinetic energy of electron = mv 2
2

1
 eV = mv 2
2
1.4 ENGINEERING PHYSICS - II

2eV
v =
m

h h h
Now    
mv 2eV 2eVm
m
m

Substituting h = 6.6256 × 1034 J-s,

e = 1.602 × 10-19 C

and m = 9.11 × 10-31 kg.,

6.6256  10 34
We get  
(2  1.602 10 19  V  9.1110 31 )1/ 2

12.26  10 10 m 12.26

=  Å
V V

So when an electron accelerated through a potential difference of 100 volt, the

de Broglie’s wavelength associated with it is 1.226 Å

Properties of matter waves

1. Lighter is the particle, greater is the wavelength associated with it.

2. Smaller is the velocity of the particle, greater is the wavelength associated

with it.

3. These waves are not electromagnetic waves.

4. Matter waves are generated by the motion of particles. If the particles are at
rest, then there is no meaning of matter waves associated with them.

5. The wavelength of matter waves are independent of charges on the particles,

but depends upon the velocity of particles.

6. The wave velocity of matter wave can be greater than the velocity of light.
QUANTUM MECHANICS 1.5

The phase or wave velocity of the matter wave is u = f where f is the frequency
of matter wave. Now, by photon analogy, the energy of the material particle,

E
E = h f (or) f =
h
Also energy of the particle by Einstein’s relation
mC 2
E = mC2 f 
h
h
Now  
mv
C2 h C2
 u  f  
h mv v
Since the particle velocity ‘v’ cannot exceed velocity of light (second
postulate of special theory of Relativity) the phase velocity of matter wave is
greater than the velocity of light].
7. The wave nature of matter introduces an uncertainty in the location of the
position of the particle because a wave cannot be said exactly at this point or
exactly at that point. However where the wave intensity is large (strong) there
is a good chance of finding the particle while where the wave intensity is small
(weak) there is very small chance of finding the particle.
8. They are pilot waves in the sense that their only function is to pilot or guide the
material particles.
9. The matter wave is not a physical phenomenon. It is rather a symbolic
representation of what we know about the particle. It is wave of probability.

1.4 EXPERIMENTAL VERIFICATION OF MATTER WAVES

Davisson - Germer Experiment
Experimental arrangement
In 1927, Davisson and Germer for the first time proved the wave nature of
electorns. The basis of their experiment was that since the wavelength of an electron is
of the order of X-rays, a beam of electrons must show diffraction effects from a crystal,
like X-rays.
1.6 ENGINEERING PHYSICS - II

(a) Experimental (b) Scattering Curve (c) Determination of

arrangement Bragg’s angle ‘’
Figure 1.1
Fig.1.1(a) shows their experimental arrangement. The electorns from a hot
filament ‘F’ are accelerated through a suitable potential difference. The narrow beam
of electrons emerging from opening P is made to strike the face of single nickel crystal
perpendicularly.
The electrons are scattered in all directions by the atoms of Ni crystal. The intensity
of electron beam scattered (i.e. number of scattered electrons) in a given direction is
measured by allowing it to enter an electron detector. The electron detector is so arranged
that it can be rotated around the nickel crystal through a large angle. The output of the
detector is measured by a sensitive galvanometer. The deflection of the galvanometer
is directly proportional to the intensity of beam entering the detector.
Observations
i) The electrons are scattered in all directions showing that they are acting like
waves. If the electrons were just particles, they would have been simply
reflected straight back.
ii) The intensity of scattered electron beam depends upon the angle ‘’ and
accelerating potential ‘V’ (Figure 1.1(b)). It was observed that high intensity
of scattered electron beam always occurred at an angle  = 50 o for 54 V
accelerating voltage. Here ‘’ is the angle between the incident and scattered
beam of electrons with respect to top surface of the crystal.
QUANTUM MECHANICS 1.7

Theory
The atomic rows of nickel crystal act like the rulings of a diffraction grating.
Under the above conditions (V = 54 volt,  = 50o), the crystal is producing the first
order Bragg reflection at an angle  = (90o - /2) where is called angle of diffraction
which is the angle between the incident beam and the crystal plane (Figure 1.1(c)). The
wavelength  of the electron wave can be calculated from the Bragg’s formula as
under:
n = 2d sin 
For first order reflection n = 1, d = a sin 25 o = interplanar distance
For nickel, interatomic distance a = 2.5 × 1010 m
 d = 2.15 × 10 10 sin 25o = 0.909 × 10 10 m
sin  = sin (90o  25o) = sin 65 o
 = 2 × 0.909 × 10 10 × sin 65o = 1.65 × 1010 m
(or)  = 1.65 Å
The theoretical value of electron wavelength can be calculated using de Broglie’s
relation.

12.26
   1.67 Å
54

Thus there is an excellent agreement between the experimental value and the
theoretical value of wavelength of electron wave. This confirms the de Broglie’s
hypothesis of matter waves.

1.5 UNCERTAINTY PRINCIPLE

In 1927, Heisenberg proposed uncertainty principle which is a direct consequence
of the dual nature of matter. It states that in any simultaneous and accurate
determination of the values of both members of particular pairs of physical variables
that describe the behaviour of an atomic system, the product of the uncertainities
h
(or) errors in the knowledge of two variables is equal to or greater than where
4π
h is the Planck’s constant.
1.8 ENGINEERING PHYSICS - II

Considering the pair of physical variables of a particle as position and momentum,

we have
px x > h / 4
where px is the error (or) uncertainity in determining the momentum along x axis and
x is the uncertainity in determining the position of the particle. Similarly
E t > h/4
J  > h/4
where E and t are the uncertainties in determining the energy and time while J and
 are the uncertainties in determining the angular momentum and angle.
Special Features
 According to the uncertainty principle it is not possible to determine
accurately and simultaneously the values of position and momentum of a
particle at any time. If we want to determine the position of an electron
very accurately, then this can only be done at the expense of accuracy in
determining its momentum and the error involved in momentum measurement
will increase.
 Thus uncertainty principle sets limits on measurement accuracy in the case of
atomic particles only and it sets no limit for heavy objects whatever on our
measuring procedures.
 The uncertainty relation shows us why it is possible for both light and matter
to have a dual, wave-particle, nature. It is because these two views so obviously
opposite to each other, can never be brought face to face in the same
experimental situation.
 Matter and light are like two faces of a coin that can be made to display either
face at will but not both faces simultaneously.
 Uncertainty principle helps us to understand several phenomena related to
sub-atomic particles. It reveals that electrons cannot exist inside the atomic
nucleus.

1.6 ELECTRON MICROSCOPE

Electron microscope uses the electron beam from electron gun as source of
radiation. Further the objective and projector lens are made from magnetic current
carrying coils. The focal length of the magnetic lenses are variable. There is one limitation
on the electron microscope such that it can work under vacuum. Any how thay have
high resolving power (resolution limit 2 Å) and high magnification power (10 6).
QUANTUM MECHANICS 1.9

There are three principle binds kinds of electron microscopes : (a) Transmission
electron microscope (TEM) (b) Scanning electron microscope (SEM) and (c) Field
emission electron microscope.
In the first two types, electron gun gives a electron beam which acts as the
source of radiation. In the last filed emission type, the specimen itself is a source of
radiation.
In the modern times, TEM is not widely used. Since the living objects can not be
studied due to vacuum. Further the preparation of replica of the specimens is a
cumbersome.
It is a type of microscope in which instead of light beam, a beam of electrons are
used to form a large image of a very small object. These microscopes ae widely used
in the field of medicine.
Principle
A steam of electrons are passed through the object and the electrons which
carries the information about the object are focussed by electric and magnetic
fields.
Since the resolving power is inversely proportional to the wavelength the electron
microscope has high resolving power because of the shorter wavelength (10 3 times
shorter than the wavelength of the visible light.
Construction

C1
Iron case

Electron gun

C2

Figure 1.2
1.10 ENGINEERING PHYSICS - II

An electron microscope is similar to that of an optical microscope. Here the

focussing of electrons can be done either by magnetic lens (or) electrostatic lens.
Normally in electron microscope magnetic lenses are used for focussing.
In general the magnetic lenses are made of two coils C 1 and C2 enclosed inside
the iron cases, which have one hole each as shown in Figure 1.2.
When the holes faces each other, the magnetic field in the space between the
two coils focus the electrons emerging out from the electron gun. Similarly the divergence
of the electrons can also be made by adjusting the position of the holes in the iron cases.

Vacuum chamber
Electron gun

Slit

Magnetic Condensing lens

B A
Object
Magnetic Object lens

A1 B1
Real image

Magnetic Projector lens

B2 A2
Final image

Figure 1.3
The essential parts of an electron microscope are as shown in Figure 1.3 and for
comparison an optical microscope is also shown aside in Figure 1.4. It consists of an
electron gun to produce, steam of electrons. Similar to condensing lens, objective and
eye piece in an optical microscope here three magnetic lenses are used, viz.
i) Condensing lens to condense the electron.
ii) Objective lens to resolve the structre of the specimen and
iii) A projector lens, similar to eye piece for enlargement.
QUANTUM MECHANICS 1.11

Light source

Slit
Condensing lens

B A
Object
Object lens
A1 B1
Intermediate image (Real image)

Projector lens
(Eye piece)

B2 A2
Final image (Virtual image)

Figure 1.4
The whole arrangement is kept inside a vacuum chamber to allow the passge of
electron beam.
Working
Steam of electrons are produced and accelerated by the electron gas. The electron
beam is made to pass through the centre of the doughnut shaped magnetic condensing
lens. These electrons are amde as parallel beam and is focussed onto the object AB
(Figure 1.3). The electrons are transmitted more in the less denser region of the object
and is transmitted less (i.e) absorbed by the more denser region of the object. Thus the
transmitted electron beam on falling over the magnetic objective lens, resolves the
structure of the object to form a magnified real image of the object. Further the image
can be magnified by the magnetic projector lens and the final image is obtained on a
fluorescent screen.
In order to make a permanent record of the image of the object, the final image is
also be obtained on a photographic plate.
1.12 ENGINEERING PHYSICS - II

Advantages
i) It an produce magnifications as high as 1,00,000 times as that of the size of
the object.
ii) The focal length of the microscopic system can be varied.
Applications
It has a very wide area of applications (e.g) in biology, metallurgy, physics,
chemistry, medicine, engineering, etc.
i) It is used in determine the complicated structure of the cyrstals.
ii) It is used in the study of colloids.
iii) In industries it is used to study the structure of textile, fibres, surface of metals,
composition of paper, paints, etc.
iv) In the medical field it is used to study about the structure of virus, bacteria,
etc., which are of smaller size.

1.7 SCANNING ELECTRON MICROSCOPE (SEM)

The surface structure or topography can be studied easily in the scanning electron
microscope than in the transmission electron microscope. The depth of focus of the
scanning electron microscope is so high that a fracture surface can be directly examined
without any polishing.
Principle
Here the image of the surface of the specimen is builtup by using an electron
probe of very small diameter which scans the surface of the specimen and collecting
the emitted secondary electrons or scattered electrons or transmitted electrons.
Construction
A high energy electron beam is produced by an electron gun (figure 1.5). The
beam is focussed to a spot of about 100Å diameter and made to scan the surface of the
specimen. The scintillator collects the secondary or scattered electrons and converts
into light signal.
The light signal is further amplified by photomultiplier and that signal is used to
modulate the brightness of an oscilloscope spot which transverse a raster in exact
syncronism with the electron beam at the specimen surface. The image observed on
the oscilloscope screen is similar to the optical image. The specimen is usually titled
towards the collector at a low angle (<30°) to the horizontal, for general viewing.
QUANTUM MECHANICS 1.13

Filament
Electron gun
Grid
Anode
st
1 condenser lens
nd Image
2 condenser lens
Scan
Scanning generator
coils Magnification
control
Objective lens

Specimen
Photomultiplier
Collector

Figure 1.5: Scanning electron microscope

Working
The high energy electron beam (30kV) is incident on the specimen surface, so
we can get back scattered high energy electrons and emitted low energy secondary
electrons (100 eV). Since the secondary electrons are of low energy they can be bent
round corners and give rise to the topographic contrast.
The intensity of backscattered electrons is proportional the atomic number and
these electrons are not so easily collected by the normal collector. If the secondary
electrons are to be collected a positive bias of 200 V is applied to the detector.
These electrons produce scintillations of light. Then it is amplified by photomultiplier
unit and is finally given to the grid of the cathode ray tube. The scanning system is in
synchronous with the scanning frequency of the specimen. Therefore during the scanning
of the fluorescent screen an optical image is created which contains the topographical
features of the surface of the specimen.
Advantages
i) It can used to examine specimens of large thickness.
ii) It has large depth of focus.
iii) It can be used to get a three dimensional image of the object.
1.14 ENGINEERING PHYSICS - II

iv) Since the image can be directly viewed in the screen, structural details can be
resolved in a precise manner.
v) The magnification may be upto 300,000 times greater than that of the size of
the object.
Disadvantages
i) The resolution of the image is limited to about 10-20 nm, hence it is very poor.
Applications
i) It is used to examine the structure of very large specimens in a three dimensional
view.
ii) Similar to the applications of electron microscope this scanning electron
microscope also has applications over various fields such as Biology, Industries,
Engineering, Physics, Chemistry, etc.

1.8 PHYSICAL SIGNIFICANCE OF THE WAVE FUNCTION ‘’

1. The wave function ‘’ measures the variations of the matter wave. Thus it
connects the particle and its associated wave statistically. It is the complex
amplitude of the matter wave.
2. The wave function or complex displacement is a complex quantity and we
cannot measure it.
3. The wave function is used to identify the state of a particle in an atomic
structure.
4. It can tell the probability of the position of the particle at a time but it cannot
predict the exact location of the particle at that time. Thus it tells us where
the particle is likely to be not where it is.
5. We can say that the wave function as probability amplitude since it is used to
find the location of the particle.
6. The probability of finding a particle in a particular volume element d is given
by
P(r) d  = |*| d = | (r, t) |² d
where * is called the complex conjugate of  Here | |² is proportional to
probability density of the particle in the state . A large value of it indicates
the high probability of the particle’s presence while a small value of it means
the small or low probability of its presence.
QUANTUM MECHANICS 1.15

7. | |² d = 1 when the particle’s presence is certain in the space.

8. Being a complex function, it does not have a direct physical meaning, but
when we multiply this with its complex conjugate, the product | |² has the
physical meaning. i.e. we will speak normally the intensity of light at a point
rather than the amplitude of light at a point since the intensity (square of the
amplitude) is a measurable and real quantity. The same thing is true for matter
waves also.

1.9 SCHROEDINGER’S WAVE EQUATION

The Schroedinger wave equation, like Newton’s laws of motion is a fundamental
equation in quantum mechanics to explain the various phenomena associated with the
atoms and molecules. Newton’s laws of motion can be applied only to macroscopic
systems and events. But the Schroedinger wave equation can be applied both to
macroscopic and microscopic systems and events. Here the wave nature of electrons
is taken into account. It is a matter wave equation. Using this equation we can get the
allowed values or eigen values of energy of electron in an atom or molecule or metal.

The classical wave equation

2y 2
2  y
 v (in one dimension) .... (1)
t 2 x 2

where y is the displacement of the particle, which is moving in x direction, at any instant
‘t’. This equation can be applied to waves in a stretched string, sound waves in air and
light waves in vacuum. The general solution of this equation is equal to

 x
y (x, t) = A exp (–i )  t –  .... (2)
 v

= A cos  (t – x/v) – iA sin (t – x/v)

Only the real part of this equation has significance in the case of stretched string
and so the imaginary part is discorded as irrelevant.

According to Schroedinger, for an atomic particle like electron, one must take the
whole solution of y, since one cannot determine the momentum and position of it
simultaneously. He called this complex displacement as wave function ‘’. Since it is a
complex, we cannot measure it.
1.16 ENGINEERING PHYSICS - II

So we specify  by

  x 
 = A exp  – i   t –  
  v 

  x  
= A exp  –2 i  t – 
  v  

  x 
(or)  = A exp  –2 i  t –   since v = 
 
.... (3)
 
The energy of a photon is given by
E = h

E
  =
h
Where  is the frequency of the radiation
Using de Broglie’s relation the wavelength of the photon is given by

h
 =
p

Where p = m v = momentum of the particle.

The same principle may be applied to electrons also.
Now equation (3) can be written as

  Et px  
 = A exp  2 i   
  h h  

  i  
= A exp     Et  px   .... (4)
  

Where h = h/2
This expression for is correct only for freely moving particles. Differentiating
partially with respect to x, we get
i
 ip ( Et  px ) ip 
 Ae 
x  
QUANTUM MECHANICS 1.17

  
(or)     p
 i x 

 2
Similarly,  2 2
 p2  .... (5)
x

  Ei
Now  
t 

h  
(or)    = E  .... (6)
 i t 
The total energy of a particle is the sum of its kinetic energy and potential energy.

p2
i.e. E = ½ mv² + V = +V ....(7)
2m
Substituting the values of p²  from equation (5) and E from equation (6) in
equation (7) we get

   – 2  2
  V
i t 2m x 2

  2  2
i.e.   – V ....(8)
i t 2m x 2
This can be written in three dimensions as

  2  2 2 2 
 ( x , y, z, t )   2  2  2   ( x , y, z , t )  V  ( x , y, z , t )
i t 2m  x y z 

  2 2
(or) i       V ....(9)
t 2m

2 2 2
Where ² =   = Laplacian operator
x 2 y 2 z 2

Equations (8) and (9) are the famous time dependent Schroedinger wave
equations in one dimension and three dimensions respectively.
1.18 ENGINEERING PHYSICS - II

Derivation of time independent Schrodinger wave equation

If we apply this equation for stationary state problems, in which the potential of a
particle does not depend upon time explicitly and the forces that act upon it and hence
V, vary with position of the particle only, we get simplified time independent
Schroedinger wave equation as follows.

Let us postulate a solution of the form

 (x, t) = (x) (t)

ipx  iEt  iEt

  
i.e. (x, t) = A e e   (x) e

 2 d 2(x )
= e–iEt/ 
x 2 dx 2

  – iE 
=    e–iEt/  (x)
t  

Substituting these values in the one dimensional equation (8) we get

2
 – iE  –  2 –iEt/  d  ( x )
i h    e–iEt/  (x) = e + V (x) e–iEt/ 
  2m dx 2

– 2 d 2( x )
E (x) – V (x) =
2m dx 2

d 2( x ) 2m
(or) + 2 ( E – V )  (x) = 0 .... 10
dx 2


In three dimensions, the above equation can be written as

2m
² +  2 ( E – V )  = 0 .... 11

Where is a function of x, y and z only.

QUANTUM MECHANICS 1.19

1.10 APPLICATIONS OF SCHROEDINGER WAVE EQUATION

1. Energy levels of an electron in an infinitely deep potential well (in one
dimension):
Consider an electron which is placed in an infinitely deep potential well with finite
width ‘a’. We assume that the movement of the electron is restricted by the sides of the
walls and the electron is moving only in the x direction; when it collides with the walls,
there is no loss of energy of the electron and so the collisions are perfectly elastic
(figure 1.6).
Since the electron is moving freely inside the well its potential energy V = 0. But
the potential energy V of the electron is infinitely high on both sides of the well and
outside the well also. Due to that the electron cannot escape from the well through the
sides.

V= V=

V=0

x=0 x=a
Figure 1.6: An one dimensional potential well
with walls of infinite height at x=0 and x=a
Boundary conditions
1. Since the potential outside the well is infinitely high, the probability of finding
the particle outside must be zero.
i.e. ||² = 0 0 > x > a
Therefore  = 0 at x = 0 and x = a
2. Inside the well the wave function is finite
i.e. ||²  0 0 < x < a
1.20 ENGINEERING PHYSICS - II

The one dimensional Schroedinger wave equation is given by

d 2 2m
 (E – V)  = 0
dx 2 2
Here V = 0 and E is simply equal to kinetic energy of electron.

d 2 2m
  E  = 0
dx 2 2
(or) d²  /dx² + k² = 0

2mE 2m p 2 4 2
where k² =  2  (using de Broglie’s relation)
2  2m 2
[k is called wave vector or wave number. | k | = 2/]
The above equation is similar to the equation of harmonic motion and so the
solution can be written as
 = A sin k x + B cos k x ....(1)
To evaluate the constants A and B we must apply the boundary conditions
namely  = 0 at x = 0 and x = a
When x = 0, we get
 = 0 = A sin(0) + B cos(0)
B = 0
When x = a,
 = 0 = A sin k a
 ka = n

n
(or) k =
a

2mE
But k² =
2

2mE n 22
 =
 2
a2
QUANTUM MECHANICS 1.21

n 2 2 2 n 2h 2
or En = 2 = ....(2)
2ma 8ma 2

nx
and  n = A sin ....(3)
a
Let us find the value of A.

a
Obviously
 |
o
n
|² dx = 1

Since the electron should exist within the well; substituting the value for n,
we get

a  nx 
A² sin ²   dx = 1

o
 a 

 2nx 
a  1  cos 
a 
A²  
 2 
dx = 1
o  
 

a
A2  a  2nx 
 x sin   1
2  2n  a  o

A 2a
i.e. = 1
2

or A= 2/a
 n 
n = 2 / a sin  
a 
x ....(4)

According to equation (2) the energy values of the electron are discrete. So that
electron will be in any one of the above energy states or eigen states n at a given time.
These energy values are often referred to as eigen values or allowed values and occur
in all quantum mechanical problems concerning spatially bound or constrained particles;
the number n is called a quantum number. The lowest eigen state is called the ground
state.
1.22 ENGINEERING PHYSICS - II

h2
Here the lowest energy level E 1 =
8ma 2

2
| 3 |
3
E3

2
| 2 |
E 2 2
| n |
E2
2
| 1 |
1
E1
0 x a a
0 x
Figure 1.7: The first three electron energy levels and their corresponding
wave functions and probability densities are represented diagrammatically.
Results
1. The energy is quantised and so it cannot vary continuously.
2. For the same value of the quantum number ‘n’, the energy is inversely
proportional to the mass of the electron and to the square of the width of the
well. The permitted energies of an electron confined in a well 1 Å wide are

n² × (6.63 × 10 -34)²
En = joule
8 × 9.1 × 10-31 × 10-20
= 38 n² eV
 E 1 = 38 eV, E2 = 152 eV, E3 = 342 eV, etc.
These energy levels are evidently quite far apart to make the quantization of
electron energy in such a well conspicious. If however the well is of macroscopic
dimensions, say 1 cm wide, the permitted electron energies are
En = 38 × 10 -16 n²eV. The permissible energy levels are now so close together
such that they may be appeared to vary in a continuous manner.
3. The probability of finding the electron in the first energy level is maximum at
thecentre of the well. But in the second energy level it is zero at the centre of
the well. Thus in each energy level, the location of finding the electron is
different (figure 1.7).
QUANTUM MECHANICS 1.23

2. Electron in a metal
Consider the same problem for a three dimensional metal in which the electrons
move in all directions so that three quantum numbers n x, n y, and n z are needed,
corresponding to the resolution of the motion into components along three perpendicular
axes x, y and z. For simplicity we will take the potential energy of the electron to be
zero inside the metal and infinite outside. So that the problem is just an extension of the
one dimensional problem discussed earlier. Therefore with a cubically shaped block of
metal of sides ‘a’ the permitted energy levels can be written as

h2
En = (nx² + ny² + nz²) .... (A)
8ma 2
where nx, ny and nz can each take any number from the set 1, 2, 3, . . . etc. irrespective
of what numbers the others take.
Similarly the wave function

8  n x x   n y y   n z z 
n , n , n = 3 sin   sin  a  sin   .... (B)
x y z a  a     a 

The three quantum numbers n x, ny and nz are required to specify completely each
stationary state. It should be noted that the energy E depends only on the sum of the
squares of nx, ny and nz.
Consequently there will be in general several different wave functions having the
same energy. For example the three independent stationary states having quantum
numbers (2, 1, 1), (1, 2, 1) and (1, 1, 2) for n x, ny and nz have the same energy value
6h 2
. Such states and energy levels are said to be degenerate and the corresponding
8ma 2
wave functions are 211, 121 and 112.
On the other hand if there is only one wave function corresponding to a certain
energy, the state and the energy level are said to be non - degenerate. For example
3h 2
the ground state with quantum numbers (1, 1, 1) has the energy and no other
8ma 2
state has this energy. The degeneracy breaks down on applying a magnetic field or
electric field to the system.
1.24 ENGINEERING PHYSICS - II

1.11 FERMI ENERGY

The expresion for the energy values given in equation corresponds to the permissible
energy values that the valence electrons in a metal may have, but it is essential to know
what energies the electrons actually possess. For a piece of metal of macroscopic
dimensions, say a centimetre cube, the energy of the ground state
(nx = ny = nz = 1) is of the order of 10 –15 eV and hence may be taken to be zero for
all practical purposes. Also the maximum spacing between consecutive energy levels is
less than 10-6 eV. So the distribution of energy levels may be regarded as a continuum.
If a plot is made for a large range of energy values such that the individual E n values
are so close together that they can be shown as a continuum and the number of states
per interval of energy, N(E) increases parabolically with increasing E as shown in
figure 1.8 (a). The dashed line shows the nature of the change in electron energies that
occurs on heating to room temperature.

0K
Fermi level EF
N(E)

At room E
temperature
E EF
(a) (b)

(a)The distribution of energy states as a function of energy E

(b) Filling of energy levels by electrons at 0 K
Figure 1.8
The valence electrons tend to occupy the lowest available energy states. However
because of the mutual interactions among all the electrons that form the electron gas, it
is necessary to consider that all the electrons are in a single system and that the Pauli
Exclusion Principle applies; according to which only two electrons can occupy a given
state specified by the three quantum numbers (n x, ny and nz), one with spin up and other
with spin down (i.e. with opposite spins). As a result of this principle, at 0 K the electrons
fill all the states upto a certain maximum energy level, E max called the fermi level or
fermi energy ‘E F’. All quantum states in the energy levels above E F are empty
(figure 1.8 (b). Thus the fermi level is a boundary line which separates all the filled
states and empty states at 0 K.
QUANTUM MECHANICS 1.25

Thus the energy of the highest filled state at 0 K is called the fermi energy
‘EF’ or fermi level. The magnitude of E F depends on how many free electrons there
are. AT 0 K all states upto E F are full and states above E F are empty. At higher
temperatures the random thermal energy will empty a few states below E F by elevating
a few electrons to yet higher energy states. No transitions to states below E F will occur
since they are full. Thus an electron cannot change its state unless enough energy is
provided to take it above E F. The probability p(E) of an electron occupying a given
energy level is represented by

1
p(E) = ((EEF ) / kT) – Fermi - Dirac distribution function .... 4.23
1 e
At 0 K, p(E) = 0 for E > EF
= 1 for E  EF
Unit probability means that the state is always full, zero probability means that it
is always empty and a fractional probability means that it is full for part of the time. It
can be seen from figure 1.9 (a) that at 0 K the electrons move about with kinetic
energies of all values upto EF. At temperatures above 0 K some electrons absorb thermal
energy and move into higher quantum states. The Pauli exclusion principle rules that an
electron can only enter an empty state, so that the thermally excited ones must go into
states above E F. Thermodynamics shows that the average allowance of thermal energy
to a particle in a system at a temperature T K is of the order kT so that only electrons
within an energy interval kT from EF, approximately, can take up thermal energy and go
to higher states with energy E F + kT (figure 1.9 (b)).

1
1.0
p(E)
p(E) 0.5

0 0
E EF E EF
kT
a. At 0 K b. At T K where T > 0

Figure 1.9: The fermi distribution curve

At room temperature kT is only 10 -2 EF or less, so that only something like 1% of
the electrons can take their allowance. That is why the specific heat of the electron gas
is much smaller than what the classical free electron theory predicts.
1.26 ENGINEERING PHYSICS - II

1.12 EFFECTIVE MASS

Effective mass of electrons in metals
Generally in most conductors m* = m since the band is only partially filled. But
the effective mass of electron in metals like Copper, Magnisium and Platinum is greater
than the mass of free electron. So if we substitute effective mass of electron instead of
true free electron mass in the expressions for specific heat, electrical conductivity and
thermal conductivity, we can get the correct values.
The concept of effective mass is able to account for many experimental
observations like high electronic specific heat of transition metals and their high
paramagnetic susceptibilities.
Effective mass of electron in semiconductors and insulators
The effective mass plays an important role in the conduction process in
semiconductors and insulators since they have full or almost filled valence bands. We
can find that the effective mass m* is negative near the zone edges of almost filled
valence bands. Physically speaking the electrons in these regions are accelerated in a
direction opposite to the direction of the applied force. This is called the negative mass
behaviour of electrons.
The electrons with negative mass can be considered as a new entity having the
same positive mass of that electron and the same positive charge as the numerical
value of the electron’s charge. The new entity is given the name ‘hole’. The advantage
of the concept of positive holes is that the momentum and current of a nearly filled band
with n empty states can be attributed to the presence of an equivalent number of n
holes with the same positive mass and positive charge of that of electron.

e je
ve

jh
h vh

Figure 1.10: Motion of electron in the conduction band

and holes in the valence band in the electric field ‘E’
QUANTUM MECHANICS 1.27

The holes are not real particles like electrons or positrons, but it is only a way of
looking at the negative mass behaviour electrons near the zone edge. We look upon the
motion of the effective negative mass electrons as the motion of the positive holes or
positive vacant sites in a nearly full band and allow the electrons in the band to carry the
current.
The positive hole conduction and effective negative electron mass conduction
are equivalent situations (figure 1.10). Calculations made on the hole picture is
advantageously retained. Several phenomena like Hall effect, Thomson effect, etc. find
ready explanation on the basis of the hole concept.

1.13 DENSITY OF STATES

Density of states ‘G(E)dE’ is defined as the number of states per unit volume in
an energy interval. E and E + dE.
No. of states between E and E + dE in a metal piece
G(E) dE =
Volume of that metal piece

nz
E
E + dE

o ny

nx

Figure 1.11: The positive octant of n - space

The number of states with a particular value of E depends on how many

combinations of the quantum numbers result in the same value of n.
1.28 ENGINEERING PHYSICS - II

Since we are dealing with almost a continuum of energy levels, we may construct
a space of points represented by the values n x, ny and nz and let each point with integer
values of the coordinates represent an energy state. Let us calculate the density of
states in a cubical metal piece with sides ‘a’. Let n x, ny and nz be the coordinate axes.
Draw a sphere in these axes with radius n² = n x² + ny² + nz² and energy E. This
sphere contains a series of shells. Each shell denotes a particular radius (or) particular
energy value. Any change in the n x, ny, and nz will change E and hence the radius ‘n’.
Suppose we want to find the number of states in between E and E + dE.
This is equivalent to say that the number of states in a shell thickness n at a
distance n in the coordinate system formed by n x, ny and nz. Since nx, ny and nz will take
only +ve values, in that sphere 1/8 of its volume will satisfy this condition. Further in
that octant we require only the shell thickness of n at a distance n.
 G = Number of states in the shell of thickness n at a distance
n from origin
= 1/8 × 4 n² n
n ² n
=
2

n 2h 2
We know that E =
8ma 2
Differentiating, we get
h2
dE = 2n dn
8ma 2
dE8ma 2
ndn =
2h 2
From equation we get
E½ (8ma 2 )½
n =
h
 E½ (8ma 2 )½ dE8ma 2
 G =
2 h 2h 2

 (8m) 3 / 2
= a³ E½ dE
2 2h 3
QUANTUM MECHANICS 1.29

Since volume of the metal V = a³,


G = (8m ) 3 / 2 V E½ dE .... (1)
4h 3
According to pauli’s exclusion principle, in each state 2 electrons can be
accommodated.
Therefore if all the states are filled up by electrons in the energy interval (between
E and E + dE) then the number of electrons per unit volume in that interval

dN = g (E) dE = 2 (8m)3/2 E ½
dE
4h 3

= (8m)3/2 E ½
dE .... (2)
2h 3
Normally all the states are not filled sates. The probability of occupation of electron
in an energy state is given by Fermi-Dirac distribution function p(E).
 dN = p(E) g (E) dE .... (3)
Calculation of density of electrons at 0 K
At 0 K, p (E) = 1
EF

  dN = 
0 2h 3
(8m)3/2 E ½
dE

 (8m) 3 / 2 E F
N =
2h 3 3/ 2
 3/2
 N = (8m) EF3/2
3h 3
number of free electros per atom  density  Avagadro number
=
Atomic weight
2/3
 3Nh 3  h 2  3N 
2/3

(or) EF =  
3/ 2  =   ....(4)
 (8m)  8m   
Hence the Fermi energy of a metal depends only on the density of electrons of
that metal.
1.30 ENGINEERING PHYSICS - II

Table 1.1: Electron density and Fermi energy of various metals

Electron density ‘N’ Fermi energy ‘EF’ at 0 K

Metal × 1028/m³ eV

Na 2.50 3.1
Ag 5.76 5.5
Cu 8.50 7.0
Zn 13.10 9.4
Al 18.10 11.6

The above table shows the values of electron density and Fermi energy of various
metals calculated from the above equations. Here we have derived the Fermi energy at
0 K. But when the temperature increases, the Fermi level or Fermi energy slightly
decreases.
It can be shown that
2
 2   
1    kT  
EF = EF  12  E F0  
0
  
and EF = kTF where EF0 is equal to Fermi energy at 0 K and T F is called
0
Fermi temperature.

1.14 ORGIN OF BAND GAP IN SOLIDS

Band gap is the net gap considering all directions along which the electrons cannot
take those values of energy that lie in that gap regardless of their direction of motion.
But this band gap disappears when there is sufficient overlap in the energy bands for
different directions.
Conduction band
Valence band
d
an
eb EV
le nc
Va
EC

a. Partially filled valence band in conductors b. Overlapping bands in conductors

Figure 1.12: Schematic band structure of conductors

QUANTUM MECHANICS 1.31

In a solid, outermost band that is fully or partially filled is called the valence band.
The band that is above the valence band and that is empty at 0 K is called the conduction
band. Solids can be classified on the basis of their band structure as conductors,
semiconductors and insulators.
Conductors are those solids which have vacant electron energy states immediately
above the highest filled level of the valence band. This can happen in two ways. In the
first case, the valance band is only partially filled as in figure 1.12(a). The electrons
here can respond to an externally applied field by acquiring extra velocity and moving
into higher energy states.
In the second case, a full valance band overlaps the conduction band as shown in
figure 1.12(b) so that the forbidden gap is zero. Monovalent metals such as the alkali
metals have one electron per atom in the outer most shell and the outer most energy
bands are half filled in these metals. Divalent metals such as magnisium have overlapping
conduction and valence bands. Therefore they can also conduct even if the valence
band is full. The band structure of trivalent metals such as Aluminium is similar to that
of monovalent metals.

Conduction band
EC
Conduction band
EC Eg = 5.4 eV
Eg = 1.1 eV
EV EV
b and
le n ce Valence band
Va
a. Energy band of silicon b. Energy band of diamond
(semi - conductor) (insulator)

Figure 1.13: Band structures of semiconductor and insulator

Semiconductors are those materials which have an energy gap of about 2 to 3 eV

or less. When the energy gap is 2eV or less an appreciable number of electrons can be
excited across the gap at room temperature. So semiconductors conduct much better
than insulators at room temperature but still orders of magnitude poorer than metals
which have no forbidden gap. By adding impurities or by thermal excitation we can
increase the electrical conductivity in semiconductors.
1.32 ENGINEERING PHYSICS - II

Insulators are those materials which have an energy gap more than 3eV. It has
been estimated that millions of volt/m of electrical potential would be necessary to
accelerate an electron sufficiently to jump the forbidden gap. The other possibility for a
transition is that electrons cross the gap by thermal excitation. At room temperature the
number of electrons that can be thermally excited across the gap in insulators such as
Diamond turns out to be extremely small. So the conductors are the materials having
enormous electrical conduction; the insulators are the materials in which practically
there is no electrical conduction and the semiconductors are the materials in which the
electrical conduction is in between the electrical conduction of conductor and insulator.
Energy Bands in Solids
Quantum free electron model gives the electrical conductivity of metals correctly.
But it is unable to give the electrical conductivity of semiconductors and other properties
of solids. Due to that the band theory of solids or zone theory of solids is developed.
According to that when an electron moving through a periodic lattice, its mass is
not only converted into its effective mass m e *, but also the band gap arises. When we
have crowded number of electrons, due to overlapping of electrons, each energy level
is splitted into N energy levels and these splitted energy levels should be accommodated
within a small region. Thus the crowded splitted energy levels appear as a band.
The band is formed only in solids.
The first allowed band is formed from K shell electrons and second allowed band
from L shell electrons. The valence electrons from the valence band which is the top
most filled band. Above the valence band there is conduction band which consists of
free electrons or conduction electrons. At 0K, there is no free electron in it. As the
temperature increases or the applied field increases the number of electrons in conduction
band will increases further.
In between the conduction band and the valence band there is forbidden gap or
band gap. The energy levels available in this gap or not allowed to occupy by the electrons
of that solid. When the band gap is more, there is little conduction. In metals there is no
band gap. So there more electrical conduction. In semiconductors, the values of band
gap are in between 0.5 eV to 2 eV. In insulators the value of band gap is more than
3 eV. The value of the band gap of semiconductor can be altered by adding or doping
some impurity atoms belonging to III group and V group of elements in the periodic
table.
QUANTUM MECHANICS 1.33

1.15 1 D SCATTERING OF ELECTRONS IN PERIODIC POTENTIAL

While the Sommerfeld theory discussed earlier accounts satisfactorily for electrical
conductivity in most metals, it failed to explain why other substances that also contain
free electrons have virtually no conductivity and are considered to be excellent insulators.
A solution to this problem is given by the Zone Theory or Band theory of solids.
The effect of the periodic lattice field on the motion of the electrons leads to the
zone or band theory of solids, which is of the greatest importance for understanding the
structures and properties of metals, alloys and non-metallic solids. According to zone
theory, the electrons move in a periodic field provided by the lattice.
The potential of the solid varies periodically with the periodicity of space lattice
and the potential energy of the electron is zero near the nucleus of the +ve ion in the
lattice and maximum when it is half way between the adjacent nuclei which are separated
by the interatomic spacing distance ‘a’.
This model was first postulated by Kronig and Penny. So taking this model and
solving the Schroedinger equation for this case, we can find the existence of energy
gap between the allowed values of energy of electron. So if we use classical theory, we
can get a parabola when we plot the curve between the electron’s energy and its
momentum.
Since the curve is a parabola, we can infer that the energy varies continuously.
But by Kronig - Penny model, we can get a parabola with some discontinuties in it as
shown in figure 1.14(b).

E Second E
allowed band B B
Forbidden band Eg
A A
First
allowed band
o k k
o
–
a

a
a. Classical free electron b. Kronig-Penny model
model energy curve energy curve

Figure 1.14: Energy Vs momentum curve

1.34 ENGINEERING PHYSICS - II

SOLVED PROBLEMS
1. Electrons are accelerated through 344 volt and are reflected from a crystal.
The first reflection maximum occurs when the angle between it and the
normal to the crystal is 40 o. Calculate the spacing between the principal
planes of the crystal. Assume the electrons are incident normal to the
crystal.
12.26 12.26
de Broglie wavelength   Å  Å = 0.66 Å
V 344
Now n  2d sin 
n
 d 
2 sin 

2  180 o  40 o
 = 70o
1  0.66
Substituting the values of  and , we get, d   0.35 Å
2  sin 70o
2. Compute the de Broglie wavelength of 10 keV neutron. Mass of one neutron
may be taken as 1.675 × 1027 kg.
Kinetic energy of neutron= 10 keV = 104 × 1.6 × 10-19 joule
= 1.6 × 10-15 joule
1/2 mv2 = 1.6 × 10-15
/ 2
 2  1.6  10 15 
 v =   27 
 1.38106 m / s
 1.67510 

h 6.625  10 34
    2.86  10 13 m  0.00286 Å
mv 1.675 10  27 1.38 10 6

3. Compute the energy difference between the first and second quantum states
for a free electron in a solid 1 metre cube.

2
n 2
x
 n 2y  n z2 
E = h 2
8 ma
QUANTUM MECHANICS 1.35

For the first quantum state nx = ny = nz = 1. Also a = 1 m

2
 6.63  10 –34  12  12  12 
 E1 =
8  9.1  10 –31  12

= 1.81 × 10–37 joule

There are many equal energy states above the first state having n x, ny and nz as
(1, 1, 2) (1, 2, 1) and (2, 1, 1).

For all these states nx2 + ny2 + nz2 = 6

2
 6.63  10 –34  6
 E2 = –31
8  9.1  10  12

= 3.62 × 10–37 joule

 E2 – E1 = 1.81 × 10–37 J

4. An electron and a bullet are independently moving with 300 metre/second,

accurate to 0.01%. The bullet mass is 0.05 kg. With what fundamental
accuracy can we locate their positions? Comment on your results.
For electron:

Momentum of electron p = mv = 9.1 × 10 -31 × 300 = 2.7 × 10 -28 kg-m/s.

The uncertainty in momentum is given to be 0.01%. Here the mass of the electron
is taken to be a constant.

(or) p = 0.0001 × 2.7 × 10 -28 = 2.7 × 10-33 kg

 The minimum uncertainty in position

h 6.6  10 34
x =   0.002 m .
p 4  2.7  10 32  4

If we consider the electron as a dot, then there is no meaning for the determination
of position of the electron with accuracy about 0.2 cm. Other wise when we
measure the momentum with accuracy about 0.01%, then we cannot locate its
position accurately.
1.36 ENGINEERING PHYSICS - II

For Bullet:

Momentum of the bullet, p = mv = 0.05 × 300 = 15 kg-m/s

and p = 0.0001 × 15 = 1.5 × 10 -3

6.6  10 34
 x = 3
 0.4  10 31 metre .
1.5  10  4

The accuracy in determining the position of the bullet is very high. This is so far
beyond the possibility of measurement and we can assert that for heavy objects
like bullets, the uncertainly principle sets no limit whatever on our measuring
techniques. Therefore the uncertainty principle is applicable to microscopic bodies
like fundamental particles.
5. A particle is moving in a one-dimensional box (of infinite height) of width
10 Å. Calculate the probability of finding the particle within an
interval of 1 Å at the centre of the box, when it is in its state of least
energy
The wave function of the particle in the ground state (n = 1) is

2 x
1  sin
L L
The probability of finding the particle in unit interval at the centre of the box
(x = L/2) is given by

2
2 2  ( L / 2) 
1   sin
 L L 
2  2
= sin 2 
L 2 L
 The probability of finding the particle within an interval of x at the centre of
the box
2
= 1 x  (2 / L) x

2  10 10
=  0.2 .
10  10 10
QUANTUM MECHANICS 1.37

6. Calculate the de Broglie wavelength of an electron accelerated to a

potential of 2 kV.

Relativistic variation of mass is not significant at 2 kV.

 Kinetic energy = 1/2 mv2 = 2 kV = 2000 × 1.6 × 10 -19 J
Mass of electron = 9.1 × 10-31 kg
 Momentum = p = 2mE
= 2  9.1  10 31  2000  1.6  10 19

de Broglie wavelength = h / mv = h / p
6.6  10 34
=
2  9.1  10 31  2000  1.6  10 19

= 2.73  10 11 m

7. Calculate the wavelength associated with a thermal neutron of energy

0.025 eV
Mass of neutron M = 1.676 × 10-27 kg. 1 eV = 1.602 × 10 -19 J
1/2 mv2 = 0.025 × (1.602 × 10-19)
or mv = [2 × 0.025 × 1.602 × 10 -19 M]1/2

h 6.62  10 34
 
mv [2  (0.025)  (1.602 10 19 )  (1.676 10  27 )]1/ 2

= 1.807 × 1010
m = 1.807 Å