Unit-I Priciples of Quantum Mechanics

UNIT – I : QUANTUM PHYSICS AND SOLIDS Applied physics
Introduction to Quantum mechanics:

Classical physics is basically based on three Newton’s laws of motion. According to
classical mechanics, the equation of motions explains the behavior of the macroscopic
particle systems. But the classical mechanic concepts cannot explain the atomic
phenomenon, stability of an atom, spectrum of hydrogen, black body of radiation,
photo electric effect, Compton Effect and Raman Effect etc.
Black body Radiation:
• A black body is body which absorbs radiations of all wavelength’s incident upon
it. It neither reflects not transmit any of the incident radiation and hence it
appears as black body.
• When black body is heated, it emits radiation which is known as black body
radiation.
• Ferry described the black body which consists of hallow thick-walled sphere
painted internally with black lamp and provided a circular small opening to enter
the radiation.
• When any radiation enters opening, it suffers
multiple reflections inside the sphere and is finally
absorbed.
• When the walls of the sphere is heated to a
temperature T, the radiation emitted from the
sphere through the opening. This is called as black
body radiation.
Spectral Distribution:
Scientists were interested to know how the energy is distributed among the different
wavelengths in the spectrum of black body.
But among all, Lummer and Pringsheim described the spectrum of the black body and
gave important findings by plotting a graph.
Vignana Bharathi Institute of Technology Page 1

• The energy of the black body is not uniformly distributed in the radiation
spectrum.
• At a given temperature, the intensity of radiation increases with increase in the
wavelength and becomes maximum at a particular wavelength ( m ). With further
increase in the wavelength, the intensity of radiation decreases.

• The wavelength corresponding to the maximum energy represented by the peak
of the curve shifts towards shorter wavelengths as the temperature increases.
From these findings it can be easily explain the black body ration.
Wien’s Law:
Wien observed the results of Lummer and Pringsheim and derived the expression for
the energy of the black bod radiation.
He explained that the wavelengths corresponding to the maximum energy ( m )
decreases as temperature increases.

Therefore mT = Constant ---------------- (1)
and E  5 = Constant ---------------- (2)
This relation is known as Wien’s displacement law.

Wien’s formula works well only for shorter wavelengths. There are considerable
deviations at long wavelengths and at high temperatures.

Rayleigh Jeans Law:

On the basis of the classical physics, Rayleigh and Jeans derived the expression for
energy density of a hot body.
8 kT
E d  = d  --------------- (3)
4
They observed that energy density increases with frequency and becomes infinite.
Rayleigh-Jeans formula agreed with long wavelengths but not works for shorter
wavelengths.
None of these two laws could explain the entire black body. The fundamental
assumptions of classical theory were fault. In 1901 Max Plank proposed a new
hypothesis known as theory of quanta.
Plank’s Radiation Law:

Max Plank explained the energy distribution in black body radiation. He derived the
radiation law using some assumptions.
1. A black body contains number of simple harmonic oscillators which can vibrate
with all possible frequencies.
2. The energy emitted from the oscillators is taken as discrete rather than
continuous.
3. The frequency of radiation emitted by an oscillator is the same as the frequency
of its vibration.
4. An oscillator cannot emit energy in a continuous manner, it can emit energy in
the multiples of a small unit called (photon). If an oscillator is vibrating with a
frequency (  ), it can only radiate in quantas of magnitudes h , i.e. the oscillator
can have only discrete energy values En, given by
En = nh = n Where  = h
5. Here n is an integer and h is plank’s constant ( h = 6.625 10−34 Joules − s ec )
6. The oscillator can emit or absorb radiation energy in packets of h values
( 0, h , 2h ,3h , 4h ,5h....nh )

If N be the total number of the Plank’s oscillators, and E be their total energy, then the
average energy per Plank’s oscillator  given by
E
 = ---------------- (1)
N
Let there be N 0 , N1 , N 2 , N3 , N 4 ,......N r etc oscillators having energy
0,  , 2 ,3 , 4 ......r etc

And E = 0 +  N1 + 2 N 2 + 3 N3 + 4 N 4 ,...... + r N r -------------- (2)
According to the Maxwell’s distribution formula, the number of oscillators having

 −r 
energy r is given by N r = N 0 exp   --------------- (3)
 kT 
Where k is Boltzmann constant.
Substituting the values of E and N values in equation (1) we get
8 h 3 1
E d =  d
c 3
exp h
kT
−1 ( ) ---------- (9)
This is known as Plank’s law of radiation.

It can also be expressed in terms of wavelength as:
c −c
= and d = d
 2
8 h  c 
3
1  c 
 E d  = 3     2 d 
c   hc   
exp   −1
  kT 
8 hc 1
E d  =  d ---------- (10)
 5
 hc 
exp   −1
  kT 
This formula agrees well with the experimental curves throughout the entire range of
wavelengths.

Derivation of Wien’s Formula from Plank’s Law:

We know that the plank’s law is
8 hc 1
E d  =  d  --------------------- (1)
 5
 hc 
exp   −1
  kT 
 hc 
Let Z =  exp   −1
5
  kT 
dz   hc    5  hc  −1  hc 
 = 5 4  exp   − 1 +     2 exp  
d    kT     kT     kT 
dz
= 0, at  = m
d
  hc    5  hc  −1  hc  
5m 4  exp   − 1 +  m   2 exp    = 0
  m kT     kT  m  m kT 
  hc    3  hc   hc 
5m 4  exp  − 
   
1 =    exp   
  m kT     kT   m kT 
  hc    1  hc   hc  
 exp   − 1  =    exp   
   kT    5m  kT   m kT  
hc
Let x =
m kT
x  x
 e x − 1 =  e x   1 − e− x =
5  5
By solving this equation, we get x = 4.96
hc
= 4.96
Therefore
m kT
hc
 mT = = cons tan t
4.96k
Which is a good agreement with Wien’s Law and also known as Wien’s Displacement
law.

Derivation of Rayleigh Jeans Formula from Plank’s Law:

 hc  hc 1 hc 1 hc 1 hc
We know that exp   = 1+ + + + + .....
  kT   kT 2!  kT 3!  kT 4!  kT
T is very high value we can neglect the higher order terms
 hc  hc
 exp   = 1+
  kT   kT
8 hc 1
Therefore, from equation (1) we get E d  =  d
 5
1+
hc
−1
 kT
8 hc 1
 E d  =  d
 5
hc
 kT
8 hc  kT
E d  = 5  d
 hc
8 kT
E d  = d  --------------------- (3)
4
Which is Rayleigh jean law and is applicable for longer wavelength.
The energy distribution curve derived by Plank theoretically represents the

experimental results accurately, i.e., it explains entire black body radiation.

Photoelectric effect:
The emission of electrons from a metal plate when illuminated by light or any other
radiation of suitable wavelength or frequency is called photoelectric emission. The
emitted electrons are called photoelectrons and the phenomenon is called photoelectric
effect.
• This phenomenon was discovered by Hertz when he allowed ultraviolet light to
fall on zinc plate.
• This phenomenon was verified by Hallwaches, Lenard, J.J. Thomson and Millikan.
• Millikan discovered that alkali metals like Na, K, Rb, and Cs eject electrons when
visible light falls on them.
• He investigated effect with a number of alkali metal over a wide range of light
frequencies.
Experimental Study of Photo-electric effect:
• A simple experimental arrangement
to study the photoelectric effect is
shown in fig.
• The apparatus consists of two photo
sensitive surfaces A and B. enclosed
in an evacuated quartz tube.
• The plate A is connected to the
negative terminal of a battery while the plate B is connected to positive
terminal of the battery through a galvanometer G.
• In the absence of any light there is no emission of the electrons and hence no
current flow through the galvanometer.
• When a monochromatic light is allowed to fall on the plate A, current starts
flowing in the circuit which is indicated by galvanometer. This current is
known as photo current.
The number of photo electrons emitted and their kinetic energy depends
upon the following factors:

1. The potential differential between the two plates.

2. The intensity of the incident radiation.
3. The frequency of the incident radiation.
4. Type of the photo metal used.
Characteristics of the photo electrons:
The effect of the potential difference (V)
For a given photo metal A, and at fixed frequency and
intensity of the incident radiation, the effect of the
potential difference (V) on the photo current (I) is
shown in fig.
• If the potential difference (V) of plate B is
increased photo electric current (I) is also
increased and reached a maximum current known as saturation current.
• Further increasing in the Voltage hardly produces any appreciable increase in
current.
• If the potential kept zero, the current still flows in the same direction.
• If the potential of the plate made negative, the photocurrent does not
immediately drop to zero due to their electromagnetic force.
• If this negative or retarding potential further increased the photo current
decreases and finally becomes zero at a particular potential.
• The negative potential difference at which the photo electric current becomes
zero is called cutoff current or stopping potential (V0).
Effect of intensity of incident radiation:

For given photo metal and fixed frequency of
incident radiation, the effect of the intensity of
radiation on photo current is shown in fig.
• If the intensity of the incident radiation is
increased from I1 to I3 and the experiment

is repeated, then the photo electric current increases in the same ratio for all
potentials.
• Saturated current is increased with increase in the intensity.
• But in all cases the stopping potential is same. i.e., the stopping potential is
independent of the intensity of the incident radiation and the saturation current
is proportional to the intensity of incident radiation.
The effect of the frequency of incident radiation:
The effect of the varying frequency of the incident
radiation while keeping the same metal and fixed
intensity of incident radiation is shown in fig.
Stopping potentials are measured for different for
different frequencies.
The graph shows that the frequency 0 the stopping potential is zero. Then the
frequency is known as threshold frequency.

Hence it can be defined as the minimum frequency ( 0 ) of the incident radiation which
can cause photoelectric emission, i.e., this frequency is just able to liberate electrons
without giving them additional energy.
The effect of Photo metal:
• The variation of stopping potential with

frequency of incident radiation is shown in
the fig.
• When the stopping potential is measure for different frequencies of different
metal surfaces, it is clear that the lines have the same slope but their interactions
with frequencies are different.
• Thus, the threshold frequency is a function of photo metal.

Fundamental laws of photo-electric emission:

1. The number of electrons emitted per second, i.e., photo electric current is
proportional to the intensity of the incident light.
2. If the frequency is less than the threshold frequency no electrons can be emitted
from the metal surface however intense the incident radiation may be. The
wavelength corresponding to the threshold frequency is called as threshold
wavelength.
3. The maximum velocity or the kinetic energy of the photoelectrons depends on
the frequency of incident radiation but not on the intensity of radiation.
4. The rate at which the electron emission from the photo metal is independent of
its temperature.
5. Electron emission from a photosensitive surface is almost instantaneous and
emission continuous as long as the frequency of incident radiation is greater than
the threshold frequency. The time lag between the incident radiation and the
emission of electrons is less than 10-8 seconds.
6. For a given metal surface, stopping potential is directly proportional to the
frequency of the incident radiation but not in the intensity of the incident
radiation.
Einstein’s Photoelectric Equation:
On the basis of quantum theory, Einstein derived an equation for the photo electric
effect known as Einstein photo electric equation.
Einstein assumed that,
• Light consists of photons or quanta of energy; energy of each photon is h .

• Each incident photon colloids with an electron inside an atom and give its all
energy to the electron.
• The part of its energy used by electron to come out of the metal surface and
remaining part of its energy is used to giving kinetic energy to the emitted
electron.

• The part of the energy which is used to eject the electron from the metal surface
is known as photoelectric work function of the metal denoted by W0.
1
Thus h = W0 + mv 2 ------------------- (1)
2
Where v is velocity of the emitted electron, this equation is known as Einstein equation
of the photo electric equation.
If the total incident energy is utilized to eject the electron from the metal surface, then
the kinetic energy of the emitted electron will be zero.
Then W0 = h0 ------------------ (2)
Where 0 is called as threshold frequency and it can be defined as the minimum
frequency which can cause photo electric emission.

Substituting the value of work function in equation (1), we get
1 2
h = h0 + mv
2
1 2
 mv = h − h0
2
1
 mv 2 = h( − 0 ) ---------- (3)
2
This is another form of Einstein’s Photo-electric equation.
This equation predicts all the experimental results.
1. For a particular metal surface work function is constant and hence
1 2
KE mv h
2
v2
Thus, the increase in the frequency of incident radiation causes increase in the velocity
of photoelectric electrons provided intensity of incident radiation is constant.
2. An increase in the intensity of incident radiation is equivalent to an increase in the
number of photons fall on the metal surface. At a frequency of incident radiation is
greater than the threshold frequency, then number of emitted electrons will
increase. Hence the intensity of emitted electrons is directly proportional to the
intensity of incident radiation.
3. If V0 is the stopping potential then the kinetic energy of the emitted electron is
equal to the potential energy of the electron.
1 2
We know that mv h h 0
2
Therefore eV0 h h 0
h h 0
V0 ------------------ (4)
e e
As h, e and 0 are constants for a given photo metal surface a
graph between stopping potential and frequency shows a
straight line with the slope h . This is same as experimental

e
results.
Wave and particle nature:
To understand the concept of dual nature, one should have
the knowledge of characteristics of particles and waves.
It easy to understand the concept of particle, since it is a physical quantity and it can be
seen. A particle has a definite mass and occupies a particular space. The characteristics
of the particle are
1. Mass (m) 2. Velocity (v) 3. Momentum (p) 4. Energy (E)
A wave can be simply defined as spreading out of the disturbance in a medium in all the
direction uniformly. It is not possible to say the wave is present here and there. The
characteristics of a wave are
1. Wavelength (  ) 2. Frequency (  ) 3. Amplitudes (A)
4. Phase (  ) 5. Wave Velocity (  ) 6. Intensity (I)
In experiments like photoelectric effect and Compton effect exhibits the particle nature,
whereas the in the experiments like interference and diffraction, it exhibits wave
nature.
Hence, we concluded that radiation is exhibiting dual nature. But it is not possible to
exhibit both the wave and particle nature at the same time.

De-Broglie Hypothesis: -
1. De-Broglie in 1924 extended the wave-particle duality to material particles like
electrons, protons, and neutrons can behave as wave.
According to his hypothesis, “A moving particle is associated with a wave with a
certain wavelength is known as De Broglie wave or matter wave”.
2. His hypothesis is based on the fact that ‘nature loves symmetry’. That is if radiation
exhibits dual nature of wave and particle; matter will also exhibit the same dual
nature.
3. According to de-Broglie a moving particle, whatever its nature, has wave properties
associated with it. He proposed that the wavelength  associated with any moving
particle of momentum p is given by
h h
= => =
p mv
Such waves associated with the matter particles are called matter waves or de-Broglie
waves.
4. De-Broglie indicated that an electron in a Bohr orbit
moving around the atom's nucleus would possess
standing waves. De Broglie used his matter-wave
hypothesis to explain quantization of atomic orbital.
5. The n full wave lengths of a de Broglie electron
wave fit around the circumference of the electron’s
circular orbit. That is n = 2 r
Expression for de-Broglie wavelength: -
According to the Planck’s and Einstein theories the energy of a photon whose frequency
 can be expressed as
E = h ------------------- (1)
Where h is the Planck’s constant.
According to Einstein’s mass energy relation
 = mc2 ------------------- (2)

From eq (1) and (2)

h = mc2
c
h = mc2

h
 =
mc
For electron we put v in place of c
------------------------------ (3)
This is called de-Broglie’s equation.

The wave length of the matter wave is inversely propositional to its momentum.
Wave length of the matter wave in terms of potential V: -
(Wave length of charged partical)
The energy of the electron in terms of potential can expressed as
E = eV ---------------------------------- (4)
The kinetic energy of an electron is
1
E = mv2 --------------------------------- (5)
2
From equation (4) and (5)
1
eV = mv2
2
Multiplying by ‘m’ in either side of the equation
1
meV = m2v 2
2
P= 2meV
Now from equation (3)
h
=
2meV
Substituting the value of h, m and e, the wavelength associate with electron
6.625  10−34
=
2  9.1  10−31  1.6  10−19 V
12.27  10−10
= m
V
Wave length of the matter wave in terms of energy E: -

If E is the kinetic energy of the electron, then
1 2 m2 v 2
E = mv 
2 2m
p2
E=  p = 2mE
2m
Now from de Broglie hypothesis the wave length of the matter wave in terms of energy
h
is  =
2mE
Properties of matter waves: -
1. The wave length of the matter wave is inversely proportional to the mass of the
particle. The larger the mass of the particle, the shorter will be the wave length
vice versa.
2. The wave length of the matter waves is is inversely proportional to the velocity of
the particle.
3. The matter waves are produced whenever the matter particle (charged or
uncharged) is in motion whereas the electromagnetic waves are produced
whenever charged particles are in motion. This property shows that the matter
waves are not electromagnetic waves.
4. The velocity of the matter wave is not constant. The velocity of the matter wave
depends on the motion of a material particle. The velocity of the electromagnetic
radiation is constant.

5. The wave nature of matter introduces an uncertainty in the location of the

position of the particle.
6. The velocity of the matter wave is greater than the velocity of light. Equating the
Einstein’s equation and Planck’s equation we, get
E = hv And E = mc 2
mc 2
hv = mc  v =
2
h
The wave velocity is w = frequency  wavelength
mc 2 h
w=  Substituting  = we get
h mv
mc 2 h c 2 c2
w=  =  w=
h mv v v
As the particle velocity v cannot exceed velocity of light c, w is greater than the
velocity of light c .
Davisson and Germer experiment: -
The first practical evidence for the matter waves was given by C. J. Davisson and L.H
Experimental arrangement: -
Germer in 1927. This was the first experimental support for De-Broglie’s hypothesis.

1. The experimental arrangement is shown in fig. it consists of three parts; they are
electron gun, target set up and circular scale arrangement. The whole
experiment is kept in vacuum.
2. The electron gun produces a fine beam of electrons of a required velocity. It
consists of filament (F), low tension battery (LTB), high tension battery (HTB) and
pin holes provided in the cylinder (C).
3. When tungsten filament ‘F’ is heated by low tension batteries (LTB) then
electrons are produced. These electrons are accelerated to a required velocity by
applying sufficient potential through the high-tension battery (HTB), across the
cylinder ‘C’.
4. The accelerated electrons are collimated into a fine beam of pencil by passing
them through a system of pin holes provided in the cylinder ‘C’.
5. The target set up help to get diffraction pattern. The target is typically nickel
crystal. The fast-moving beam of electrons from electron gun is made to incident
on the nickel target, which can be rotated about an axis perpendicular to the
plane of the diagram.
6. The electrons are reflected in all possible directions by atoms at lattice points in
the surface planes, which acts as a diffraction grating.
7. In the circular scale arrangement, an electron collector is fixed to a circular scale
which can collect the electrons and can move along the circular scale. The
electron collector is connected to a sensitive galvanometer to measure the
intensity of electron beam entering the collector.
Calculation of the wavelength associated with electrons: -
When a potential of 54v is applied the first order diffraction maximum is observed at
angle of 500 between incident and reflected rays.
It can be observed in the plot of variation of number of scattering electrons with the
angle of diffraction as 650.
The inter planar spacing (d) of nickel crystal is 0.091nm, which is measured by the x-ray
diffraction method.

Applying Bragg’s law 2d sin  = n
 = 650
We know that d = 0.091nm
n =1
Now from the Bragg’s law equation, we get
 = 1.648A0
The de-Brogile wavelength associated with the electron, when a potential difference of
54v is applied.
According to de-brogile wave length
12.26 12.26
= = = 1.66 A0
V 54
The wavelength of the electron beam calculated from Bragg’s law and de-Brogile’s
equation are in good agreement. Hence the wave nature of the particle is proved
experimentally.
The drawback of this experiment is that whether the diffraction pattern formed is due
to electrons (or) electromagnetic radiation generated by fast moving electrons are not
known.
Heisenberg’s uncertainty principle: -
In 1927 Heisenberg proposed a very interesting principle known as uncertainty principle
as a consequence of the dual nature of the matter.
Statement: -
It is impossible to determine precisely and simultaneously the value of pair of
physical variables which describe the motion of an atomic system

1. According to “uncertainty principle” if we obtained a perfect knowledge of the

position of an electron, we have no way of knowing its momentum, and the vise-
verse.
2. If particle is moving based on classical mechanics, at any instant we can find its
position and momentum. In wave mechanics, we regard a moving particle as a wave
group. The particle that corresponds to this wave group may be located anywhere
within the group at any given time.
3. In the middle of the group, the probability of finding the particle is more but the
probability of finding the particle at any other point inside the wave group is not
zero.
4. Narrow the wave group higher will be the accuracy of locating the particle. At the
same time, one cannot define the wavelength  of the wave accurately when the
 h
wave group is narrower. Since measurement of particle’s momentum  =  also

mv 
becomes less accurate.
5. On the other hand, when we consider a wide wave group, wavelength  can be well
defined and hence measurement of momentum becomes more accurate, at the
same time, since the width of the wave group is large, locating the position of the
particle becomes less accurate.
6. If x and p are the uncertain in the position and momentum measurements then,
according to uncertainty principle
h
x p 
4
Another form of the uncertainty is in energy and time. If the energy is emitted in the
form of electromagnetic waves, we cannot measure the frequency v of the waves
accurately in the limited time available.
1
Since v 
t
Hence the corresponding uncertainty in energy E is
E = hv

h
And so E 
t
Or E t  h
A more precise calculation based on the nature of wave group modifies this result to
h
E t 
4
This gives uncertainty in the measurement of an energy and time of a process.
Schrödinger wave equation: -

In 1926 Schrödinger presented wave equation by using de Broglie ideas of matter
waves. The Schrödinger ‘s equation is the fundamental equation of quantum mechanics.
It is the differential equation for the de-broglie waves associated with particles and
describes the motion of the particles.
Schrödinger introduced a mathematical function  ( x, y, z, t ) which is the variable
quantity associated with the moving particle, and is a complex.  is called “wave
function” as is characterizes the waves associated with the particle.
If a particle of mass ‘m’ moving with a velocity ‘v’ is associated with group of waves. Let
us consider a simple form progressing wave traveling in positive x-direction as time t is
 =  0 sin ( t − k x) ------------------ (1)
Where = (x,t) and

 0 is amplitude.
Differentiating  partially with respect to x twice,
2
=− k 2
 0 sin ( t − k x)
x2
= −k 2
 2
 +k 2
 = 0 -------------------- (2)
x2
2
Where k is wave number and is given as k =


Equation (2) is the differential form of the classical wave equation. Now we incorporate
h
de Broglie wavelength  = and k into equation (2).
mv
Then we obtain
 2  4 2 m2 v 2
+  = 0 ----------------------------- (3)
x2 h2
The total energy E of the particle is sum of its kinetic energy K and potential energy V,
i.e. E = K+V ------------------------------------ (4)
1
and K = mv -------------------------------------- (5)
2
2
m 2
v 2 = 2 m ( E − V ) ----------------------------------- (6)
Substituting equation (6) in equation (3)

 2  8 2
m(E − V )
+  =0
x2 h2
h h
In quantum mechanics, the value occurs most frequently. Hence, we denote h = .
2 2
Using this notation, we have
2 2 m ( E − V)
+  = 0 ------------------------------ (7)
x 2
h2
Where= (x,t) .
 2   2   2  2 m ( E − V)
+ + +  = 0 ------------------------- (8)
x2 y2 z2 h2
Using Laplacian operator,

2 2 2
 =2
+ + -------------------------------- (9)
x2 y2 z2
The equation (9) can be written as
2 m ( E − V)
 2
 +  =0
h2
This is Schrödinger time independent wave equation.

Born interpretation on  (OR)

Physical significance of the wave function ( ): -
1. The probability that a particle will be found at a given place in space at a given
instant of time is characterized by the function (x, y, z,t).It is called the wave
function. This function can be either real or complex.
2. A satisfactory interpretation of the wave function  associated with a moving
particle was given by Born in 1926. He postulated that the square of the magnitude
of the wave function  (or)  * evaluated at a particular point at any instant

2
represents the probability of finding the particle at that point.
3.  is called the ‘probability density’ and  is the ‘probability amplitude’. According

2
to this interpretation, the probability of finding the particle within an element of
volume d (dxdydz) is  d , since the particle is certainly somewhere in space. So,

2
the integral of  d overall space must be unity, that is  d=1

2 2
The wave function that obeys this equation is said to be ‘normalized’.

4. There are certain limitations for  :-
(1)  must be finite everywhere: – if for instance  is infinite for a particular point, the
same would be true for the wave function * . It would mean an infinitely large
probability of finding the particle at that point. This would violate the uncertainty
principle. Therefore  must have a finite or zero value at any point.
(2)  must be single-valued: - If  has more than one value at any point, it would
mean more than one value of probability of finding the particle at that point which is
obviously ridiculous.

(3)  must be continuous and have a continuous first derivative every where
d 2
It necessary for the Schrödinger equation is that must be finite everywhere. This
dx 2
d d
can be so only if has no discontinuity at any boundary. So is a continuous
dx dx
function then  is also continuous across the boundary.
Particle in one dimensional potential box: -

Consider a particle moving inside a box along the X-direction. The particle is bouncing
back and forth between the walls of the box. The box has potential barriers at X=0 and
X=L i.e., the box is supposed to have walls of infinite height at X = 0 and X = L. the
particle has mass m and its position x at any instant is given by 0 < X< L.
The potential energy V of the particle is infinite on both sides of the box. The potential
energy V of the particle can be assumed to be zero between X = 0 and X = L.
In terms of the boundary conditions imposed

by the problem, the potential function is
V = 0 For 0 < X < L
V =  For X  0
V =  For X  L
The particle cannot exist outside the box and

so its wave function  is 0 for X  0 and X  L . Our task is to find what  is within the
box i.e., in between x = 0 and x = L. Within the box, the Schrödinger’s equation becomes
d 2  8 2 m
+ E  = 0 ----------------------- (1)
dx2 h2
82mE 2
Putting =k , the equation becomes
h2
d 2
+k 2
 = 0 ------------------------------ (2)
dx2
The general solution of equation (2) is
 = A sin k x + B cos k x -------------------- (3)

The boundary conditions can be used to evaluate the constants A and B in Eq (3).
 = 0 at x = 0 and hence B = 0
 = 0 at x = L . Hence 0 = A sin k L
n
Since A  0 , kL= n where n is an integer or k =
L
n x
Thus  n ( x ) = A sin ----------------------------- (4)
L
The energy of the particle
k 2h2 h2n2 2
En = = ----------------------------- (5)
8 2 m L 2 8 2 m
n2h2
E n = ---------------------------------- (6)
8mL 2
For each value of n, there is an energy level and the corresponding wave function is
given by Equation (4).
Each value of En is called an Eigen value and corresponding  n is called wave function.
Thus, inside the box the particle can only have discrete energy values specified by
equation (6). Note that particle cannot have zero energy.
The value of ‘A’ in equation (4) can be obtained by applying normalization condition.
Since the particle is inside the box of length L, the probability that the particle is found
inside the box is unity.
L
   d x =1
*
0

L n  x
  =1
2 2
A sin 
0
 L 
 2n x
 1 − cos L dx=1

0 
L
2
A 
 2 
 
L
 A2 =1
2
2
 A=
L

The normalized wave functions of the particle
2 n x
=  n = sin
L L
The normalized wave functions 1 ,  2 and  3

and corresponding probability density
functions  n are plotted in fig.

2

Solids:
Free electron theory, Drude and Lorentz theory:
Introduction:
In solids, electrons in outer most orbits of atoms determine its electrical properties.
Electron theory is applicable to all solids, both metals and nonmetals. In addition, it
explains the electrical, thermal and magnetic properties of solids. The structure and
properties of solids are explained employing their electronic structure by the electron
theory of solids. It has been developed in three main stages.
1. Classical free electron theory
2. Quantum Free Electron Theory.
3. Zone theory.
1. Classical free electron theory:
The classical free electron theory was proposed by Drude and Lorentz in 1900.
According to this theory, metal contains free electrons which are responsible for the
electrical conductivity and electrons obey the laws of classical mechanics.
Assumptions (or) Salient features in classical free electron theory:
• In metals there are a large number of free electrons moving freely in all possible
directions.
• These free electrons behave like gas molecules in a container obeying the laws of
kinetic theory of gases.
• In the absence of field, the energy associated with each electron at a temperature T
3 1
is given by
3
KT . It is related to kinetic energy as KT = mv 2
2 2 2
Where v is the thermal velocity and K is Boltzmann constant.
• In metals, the positive ion cores are at fixed positions and the free electrons move
randomly and collide either with positive ion cores or with other free electrons or
with boundaries. Hence these collisions are elastic. Therefore, the electric
conduction is due to free electrons only.
• Electron velocities in a metal obey Maxwell-Boltzmann distribution of velocities.
• The free electrons move in a constant potential field. Hence the potential energy of
the electrons is constant.
• When an electric field is applied to a metal, free electrons are accelerated in the
direction opposite to the direction of applied electric field with a velocity called drift
velocity represented as vd.
Advantages or Merits classical free electron theory:
• It verifies ohm’s law.
• It explains electrical and thermal conductivities of metals.
• It derives Widemann-Franz law.
• It explains optical properties of metals.
Limitations or drawbacks or Demerits classical free electron theory:
• It fails to explain the electrical conductivity of semiconductors and insulators.
• It fails to explain the temperature variation of electrical conductivity at low
temperature.
• It fails to explain the concept of specific heat of metals.
• It fails to explain the mean free path of the electrons.
• The phenomenon like photo electric effect, Compton effect and black body
radiation could not be explained by classical free electron theory.
• It fails to explain temperature dependence of paramagnetic susceptibility and
ferromagnetism.
2. Quantum Free Electron Theory:
In 1928 Sommerfeld developed the quantum free electron theory. According to
Sommerfeld, the free electrons move with a constant potential. This theory obeys
quantum laws.
Assumptions of Quantum Free Electron Theory:
• Valence electrons move freely in a constant potential within the boundaries of metal
and is prevented from escaping the metal at the boundaries (high potential). Hence
the electron is trapped in a potential well.

• The distribution of electrons in various allowed energy levels occurs as per Pauli
Exclusion Principle.
• The attraction between the free electrons and lattice ions and the repulsion
between electrons themselves are ignored.
• The distribution of energy among the free electrons is according to Fermi-Dirac
statistics.
• The energy values of free electrons are quantized.
• To find the possible energy values of electron Schrodinger time independent wave
equation is applied. The problem is similar to that of particle present in a potential
box.
n2 h2
• Energy of electron is En = , where n = 1, 2,3,...
8mL2
Merits of quantum free electron theory:
• It successfully explains the electrical and thermal conductivity of metals.
• It can explain the Thermionic phenomenon.
• It explains temperature dependence of conductivity of metals.
• It can explain the specific heat of metals.
• It explains magnetic susceptibility of metals.
• It can explain photo electric effect, Compton Effect and block body radiation etc.
• It gives the correct mathematical expression for the thermal conductivity of metals.
Demerits of quantum free electron theory:
• It is unable to explain the metallic properties exhibited by only certain crystals.
• It is unable to explain why the atomic arrays in metallic crystals should prefer certain
• structures only.
• This theory fails to distinguish between metal, semiconductor and Insulator.
• It also fails to explain the positive value of Hall Co-efficient.
• According to this theory, only two electrons are present in the Fermi level and they
are responsible for conduction which is not true.

3. Zone theory or Bloch theory:

This is theory is proposed by Bloch. A crystalline solid consists of a lattice, which is
composed of a large number of ion cores at regular intervals, and the conduction
electrons that can move freely throughout the lattice. The conduction electrons move
inside periodic positive ion cores. Hence instead of considering uniform constant
potential inside the metallic crystal, the periodicity of the lattice is to be considered,
and hence the electrons move in periodic potential.
The potential is minimum at the positive ion sites and maximum between the two ions.
The one-dimensional Schrödinger equation corresponding to this can be written as
 2 8m 2
+ 2 ( E − V ( x) ) = 0 ----------(1)
x 2 h
The periodic potential V(x) may be defined by means of the lattice constant as
V ( x) = V ( x + a) ----------(2)
Bloch has shown that the one-dimensional solution of the Schrödinger equation is of the
form.
 ( x) = exp(ikx)U k ( x)----------(3)
In the above equation Uk(x) is called “modulating function”. Because free electron wave
is modulated by Uk(x) is periodic with the periodicity at the crystal lattice. Let us now

consider a linear chain of atoms of length “L” in one-dimensional case with “N” number
of atoms in the chain. Then,
U k ( x) = U k ( x + a) ----------(4)
Where “a” is a lattice distance.
From equation (3) and (4), we have
 ( x + Na) = U k ( x + Na).exp ik ( x + Na)
= U k ( x).exp ikx.exp ikNa
=  ( x) exp(ikNa )
  ( x + Na) =  ( x) exp(ikNa) − − − − − (5)
This is referred to as Bloch condition. Similarly, the complex conjugate of (5) can be
written as
 *( x + Na) =  *( x) exp(−ikNa) − − − − − (6)
From equations (5) & (6)
 ( x + Na)  *( x + Na) =  ( x) exp(ikNa) *( x) exp(−ikNa)

 ( x + Na)  *( x + Na) =  ( x) *( x)
( exp(ikNa)e xp( −ikNa) = e0 = 1)
 ( x + Na ) =  ( x)
2 2
This means that the electron is not localized around one’s particular atom and the
probability of finding the electron is same throughout the crystal.
2. Kronig – Penny Model: -

According to this theory the electrons moves in a periodic potential produced by
the positive ion cores. The nature of the energies of the electron is determined by
solving Schrödinger wave equation. For simplicity, the periodic potential is taken in the
form of a regular one-dimensional array of square well potentials. This is called
“Kronig – Penny model”. It consists of two series of regions labeled I and II.

The corresponding Schrödinger equations for the two regions I and II are
Region I:
 2 2m
+ 2 E = 0
x 2
2mE
Let a2 = 2
 2 2m
thus + 2 E = 0 ------ (1)
x 2
Region II: V = V0
 2 2m
+ 2 ( E − V0 ( x) ) = 0
x 2
2m
Since V0  E , Let 2 (V0 ( x) − E ) =  2
 2
Thus, −  2 = 0 ------- (2)
x 2
According to Bloch theorem solutions of above Schrödinger eq’s have the form,
 ( x(a + b) ) =  ( x).exp[ik (a + b)] ------- (3)
 * ( x(a + b) ) =  *( x).exp[−ik (a + b)] ------- (4)

This requires both and to be continues throughout the crystal. Applying

boundary conditions for the above solution,
We obtain,
P sin a
+ cos  a = cos ka ------- (5)
a
m Vob a
Where scattering power, is given as P = 2
And Vob is a measure of potential barrier Strength.

The left-hand side of the equation (5) is plotted as a function of αa. This is shown in
fig. The cosine form on the Right-hand side of the equation can only have values
between –1 and +1 as indicated by horizontal lines in the fig.
Schematic representation of eq.5 is shown as,
Therefore, the equation (5) is satisfied only for those values a for which left hand side
lies between ±1. This means some ranges of energies are allowed and some other
ranges are not allowed.
From the above figure the conclusions are
1. The energy spectrum of the electron consists of a number of allowed and

forbidden energy bands.

2. The width of the allowed energy band increases with increase of energy values
i.e., increasing the values of a. This is because the first term of equation (5)
decreases with increase of αa
3. With increasing P i.e., with increasing, potential barrier, the width of an allowed
band decreases.
As P →  , the allowed energy region becomes infinitely narrow and the energy
spectrum is a line spectrum.
If P →  then equation (5) has the only solution.

i.e., sin a → 0
 a =  n
 n
 =
a
n 2 2
 =2
a2
2mE
But a 2 = 2
n 2 2 2mE
 = 2
a2
n 2 2 2
E= 2
a 2m
n2 h2
or E = --------- (6)
8ma 2
This expression shows that the energy spectrum of the electron contains discrete
energy levels separated by forbidden regions.
This is the result we obtain for a particle in a box of atomic dimensions with a constant
potential i.e., electron tightly bound and tunneling through the barriers becomes
improbable. This shows the case of an insulator.

If P → 0 , then
 cos  a = cos ka
  a = ka
 = k
2 = k2
 2 
2
2mE
But  = 2
and k = 
2

  
2
 2 
2
2mE
 = 
  
2
2mE ( 2 )  2 
2 2
= 
h2   
8m 2 E 4 2 h
= but  =
h2 2 mv
8m 2 E 4 2 (mv) 2
 =
h2 h2
1
 E = mv 2 − − − − − (7)
2
The equation (7) shows all the electrons are completely free to move in the
crystal without any constraints. Hence, no energy level exists. This case supports the
classical free electron theory.
The electrons first occupy the lower energy bands and are of no importance in
determining many of electrical properties of solids. Instead, the electrons in the
higher energy bands of solids are important in determining many of the physical
properties of solids. Hence, we are interested in those two allowed energy bands
called Valence and Conduction Bands.
The band corresponding to the outer most orbits is called Conduction Band and
the next inner band is called Valence Band. The gap between these two allowed
bands is called forbidden energy gap (or) Band gap. Normally we are interested in the
valence band occupied by valence electrons. Since they are responsible for the origin
of energy Band Formation.
Origin of energy band formation: -

In an isolated atom, the electrons are tightly bound and have discreet, sharp energy levels
as shownfig.1.
When two identical atoms are brought closer the outer most orbits of these atoms overlap
and interact, the energy levels corresponding to those energy levels spilt in to two.
If more atoms are brought together more levels are formed, since the levels are so close to
each other that they form an almost continuous band.
The width of this band depends on degree of overlapping of electrons.
In solids many atoms brought together and forms very closely spaced levels with forbidden
energy gaps between them as illustrated in fig.2.
Overlapping of the bands occurs for smaller equilibrium spacing r0.

The electrons first occupy the lower energy bands which have no importance in
determine many of the electrical properties of solids; instead, the electrons in the
higher energy bands of solids are important in the determination of many physical
properties.
The band corresponding to the outer most orbits is called conduction band and the
next inner band is called valence band and the gap between these two allowed
bands is called forbidden energy gap or band gap.
Classification of Solids into metals, semiconductors and Insulators: -

According to band theory, the electrons in a solid can be possess bands of energies
called allowed bands of energies and these electrons may not possess some other
bands od energies called forbidden bands od energies.
The allowed bands of energies and are present alternatively one after another for the
electrons of a solid. The top most band is called conduction band and the next band
below conduction band is valance band. These two bands are separated by forbidden
band.
Valence Energy Band
The electrons which are found in the outermost shell are called Valence Electrons.
These valence electrons are usually formed by a series of energy levels which in turn
makes the valence band. This valence band is known to have the highest level of
occupied energy.
Conduction Energy Band
Because the valence electrons are not strongly bound to the nucleus, a few of them exit
the outermost orbit and become free electrons even at ambient temperature.
A conduction band has the lowest occupied energy levels and contains conduction
electrons.

Forbidden Energy Gap

There is an energy space between the conduction and valence band, this energy space is
known as the forbidden gap. This band doesn’t allow the electron to exist at all. This
results in zero electron flow in this band.
This forbidden gap allows the electron to travel from the valence to the conduction
state.
Based on the forbidden gap in the solids it can be classified into three categories.
1. Conductors 2. Insulators 3. Semiconductors.
Conductors
Conductors are made up of the material in which the valence band or the forbidden
energy gaps vanish. Then the conduction band and valance band are overlapped with
each other. Therefore, there is a high number of free electrons available at room
temperature.
Examples: Gold, Alluminium, Silver, Iron and Copper.
Features of conductors are as follows:
1. There is no energy gap due to both conduction and the valence bands overlap
with each other.
2. The conduction rises when the voltage gets increased.
3. For power transmission there are high numbers of free electrons.
4. It has positive temperature coefficient.

Insulators
The substances which do not conduct electricity and do not allow the electricity to pass
through them are known as Insulators. The prohibited energy gap is big enough to not
allow the electricity to pass through them.
Examples: Rubber, Mica, paper and wood etc.
The features of the insulators are as follows:
1. The energy gap is in the insulators which has a value between 6 - 10 eV.
2. Electrons are strongly packed together in the valence band.
3. It has negative temperature coefficient.
Semiconductors
The materials which have conductivity between conductors and the insulators are called
Semiconductors. In semiconductors, electricity can only be conducted if there is energy
which is applied externally, because the energy gap is tiny.
Examples: Germanium, Silicon etc
Properties of semiconductors are as follows:
1. The energy gap in semiconductors varies depending upon the material. The
prohibited energy gap for silicon is 1.1eV while on the other hand for Germanium
it is 0.8eV.
2. As the temperature increases the connectivity rises in the semiconductors.
3. At absolute zero temperature they act like insulators.
4. They have negative temperature coefficient.

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UNIT – I : QUANTUM PHYSICS AND SOLIDS Applied physics

Introduction to Quantum mechanics:

Vignana Bharathi Institute of Technology Page 1

increase in the wavelength, the intensity of radiation decreases.

decreases as temperature increases.

and E  5 = Constant ---------------- (2)

This relation is known as Wien’s displacement law.

Vignana Bharathi Institute of Technology Page 2

Rayleigh Jeans Law:

Plank’s Radiation Law:

Vignana Bharathi Institute of Technology Page 3

0,  , 2 ,3 , 4 ......r etc

According to the Maxwell’s distribution formula, the number of oscillators having

This is known as Plank’s law of radiation.

Vignana Bharathi Institute of Technology Page 4

Derivation of Wien’s Formula from Plank’s Law:

Vignana Bharathi Institute of Technology Page 5

Derivation of Rayleigh Jeans Formula from Plank’s Law:

The energy distribution curve derived by Plank theoretically represents the

Vignana Bharathi Institute of Technology Page 6

Vignana Bharathi Institute of Technology Page 7

1. The potential differential between the two plates.

Effect of intensity of incident radiation:

Vignana Bharathi Institute of Technology Page 8

frequency is known as threshold frequency.

The effect of Photo metal:

• The variation of stopping potential with

Vignana Bharathi Institute of Technology Page 9

Fundamental laws of photo-electric emission:

• Light consists of photons or quanta of energy; energy of each photon is h .

Vignana Bharathi Institute of Technology Page 10

Then W0 = h0 ------------------ (2)

Where 0 is called as threshold frequency and it can be defined as the minimum

frequency which can cause photo electric emission.

graph between stopping potential and frequency shows a

straight line with the slope h . This is same as experimental

Vignana Bharathi Institute of Technology Page 12

 = mc2 ------------------- (2)

Vignana Bharathi Institute of Technology Page 13

From eq (1) and (2)

This is called de-Broglie’s equation.

Wave length of the matter wave in terms of energy E: -

Vignana Bharathi Institute of Technology Page 15

5. The wave nature of matter introduces an uncertainty in the location of the

Vignana Bharathi Institute of Technology Page 16

Vignana Bharathi Institute of Technology Page 17

Applying Bragg’s law 2d sin  = n

Vignana Bharathi Institute of Technology Page 18

1. According to “uncertainty principle” if we obtained a perfect knowledge of the

Vignana Bharathi Institute of Technology Page 19

Schrödinger wave equation: -

Where = (x,t) and

Differentiating  partially with respect to x twice,

Vignana Bharathi Institute of Technology Page 20

Substituting equation (6) in equation (3)

Using Laplacian operator,

The equation (9) can be written as

 ( x + Na)  ( x + Na) =  ( x) exp(ikNa) ( x) exp(−ikNa)