UNIT – I QUANTUM MECHANICS

Classical Mechanics:-
It is the branch of physics, which explains the motion of macroscopic objects. It was
introduced by sir Issac Newton.
Quantum Mechanics:-
It is the branch of physics which explains about the motion of microscopic particles like
electrons, protons etc. It was introduced by Max Planck in 1990.

Blackbody radiation
When a body is heated , it emits thermal radiation which is electromagnetic in nature
and its energy is smoothly distributed over all wavelengths. It produces continuous
spectrum.
Def: The radiation emitted by the source by virtue of its temperature is called
thermal radiation.
Def: A body that absorbs the entire radiation incident on it is called a perfect blackbody.
When a perfect blackbody is heated, it emits radiation at all frequencies and thus, it is a
good radiator as well as a good absorber. In practice, there are no perfect blackbodies.
Def: The radiation emitted by a perfect blackbody is called blackbody radiation.
Construction
An ideal black body can be made by taking a hollow sphere (cavity) and drilling a
small hole in it (see Fig. 1). Its inner surface is coated with lampblack. Any radiation
entering the cavity through O is incident on the inner surface of the cavity and is partly
absorbed and partly reflected. The reflected component is incident at another point on
the inner surface, where again it is partly absorbed and partly reflected. Thus, light
entering the cavity undergoes multiple reflections at the walls and is trapped inside the
cavity. Hence, the hole acts a perfect absorber and appears perfectly dark

Fig 1 Black body

 Conversely, when the cavity is heated, the radiation produced in the
cavity comes out through the aperture and contains all the wavelengths.

:
Therefore, the hole acts as a perfect emitter and has the characteristics of
blackbody radiation. Its spectrum can be analyzed by an infrared spectrometer
:
and the emissive power of the blackbody at different wavelength can be
determined.
:
Figure 2 shows the distribution of radiant energy as a function of
:
wavelength at different temperatures. It shows that at a given temperature the
radiation energy density initially increases with increasing wavelength at
:
particular wavelength λm, and after that decreases finally to zero at very high
wavelengths. The spectral distribution of that radiation is a function of
: and not on the material.
temperature alone

.
'
a
n
d

Fig. 2 Radiation energy density versus wavelength at a given temperature

Laws of Blackbody Radiation

The following are various Laws of blackbody radiation.

1. Stefan-Boltzmann law:

The total radiation emitted from a blackbody at temperature T is proportional

to the fourth power of the absolute temperature of the body T4.

E= T4 …………(1)

where is called Stefan's constant having a numerical value of 5.67 x 10-8

W/m2 –K4 .
2. Wien's law:

The peak wavelength, A.max at whic the maximum emission occurs for
any given temperature is inversely proportional to the absolute temperature of the
body.
3

Thus, …………(2)

3. Rayleigh-Jean's Law and the Ultraviolet catastrophe:

In calculating theoretically the frequency distribution of thermal radiation,

it was assumed that a blackbody was made up of a huge number of atoms and the
atoms are regarded as small harmonic oscillators. The random thermal motion of
atoms emits thermal radiation from the black body.

According to Boltzmann's principle of equipartition of energy, each simple

harmonic oscillator has an average thermal energy of 'kT' at thermal equilibrium.
Rayleigh assumed that each of the standing waves should have energy 'kT . He
derived an expression for the energy density of radiation distribution within the
cavity

…………….(3)

Equation (3) is known as Rayleigh – jeans law.

The energy density calculated agrees well with the experimental results at
longer wavelength not at shorter wavelength.

As the intensity of the thermal radiation should increase with square of

frequency at large portion of UV rays, this contrary to our experience and
violates the conservation of energy. This contradiction came to be
known as ultraviolet catastrophe. This was the first indication of inadequacy of
classical physics.
4. The Planck's Radiation Law:

It states that electromagnetic radiation from heated bodies is not emitted as

a continuous flow but is made up of discrete units or quanta of energy, the size of
which involves a fundamental physical constant (h), and the formula is given by

……..(4)
Planck's radiation law

In 1900, Planck put forward a revolutionary postulate that

an oscillating atom can absorb or reemit energy only in quantities
that are integer multiples of 'hʋ'. All other values of energy are not
allowed. The energies of the molecular oscillators must be
quantized, not continuous.

Derivation of Planck's law:

The number of oscillators in an energy state En = nhʋ is

determined by the Maxwell-Boltzmann distribution function.

Nn = N0 e-En/KT……..1

where N0 is the number of oscillators in the ground state (En = 0).

Let there be N oscillators in the system in equilibrium at absolute

temperature T. According to Maxwell-Boltzmann distribution law,
the number of oscillators Nn with energy En is given by

Nn = N e-En/KT ……2

Since the energies of the oscillators assume discrete values, we

have to sum over all possible oscillator states to determine (E).

The average energy (E) of an oscillator is then given by

…………..2

Substituting the value for n=0,1,2,..

Substituting = , we get
 ……………..3

we know that = , substituting in eq (3), we get

…………4

The number of oscillators in the frequency range ʋ and n+dʋ are

estimated to be

Above eq multiply by eq (4) average energy oscillator; Planck’s

obtained the energy density in black body radiation

In terms of frequency

In terms of wavelength

Eq (5) is known as Planck’s radiation law, which gives complete

information with the experimental observations at all wavelength and for
all temperature.
Photoelectric effect

In 1887, Hertz discovered that electron is ejected when ultraviolet

radiation strikes a metal surface.
Definition:
Photoelectric effect is the phenomenon in which electrons are knocked off
a metal surface when light is incident on it (Fig.1). The metal is said to be a
photosensitive material and the liberated electrons are called photoelectrons.
Construction:
Electronic emission increases with the intensity of the radiation
falling on the metal surface. For each substance, there is a minimum frequency
n0 of light and for light of frequency less than n0, photoelectrons are not
produced, however intensity of the incident light may be.
The minimum frequency n0 is called threshold frequency.
0

Fig 1 Photoelectric effect

The photoelectrons that are emitted are found to have a range of
energies. The maximum kinetic energy of the photoelectrons varies with the
frequency of the incident light (Fig.2) and is independent of the intensity of the
light.
Einstein's explanation:
In 1905, Einstein's successfully explained the photoelectric effect by
treating incident light as a stream of photons. In a beam of monochromic light of
frequency, n, all photons have the same energy hυ. When the photons
encounter electrons in a metal, they give up their energy to the electrons. As the
electrons are held within the metal by a potential barrier at the surface, an
electron should have enough energy to overcome from the metal. This work
function 1s specific for the metal.
When an electron absorbs a photon, it gains energy equal to hʋ. If
the electron will escape from the metal.
 Thus, out of the total energy hn, a small portion, Wo is spent on
overcoming the potential barrier and the balance energy ( - ) is given to the
electron as kinetic energy. Applying the law of coservation of energy to this
phenomenon,

Equation (1) is known as Einstein's photoelectric equation.

Fig.2 Kinetic energy of the photoelectrons versus the frequency of the incident light

In 1916 Millikan verified Einstein's theory. If a plot is drawn between the

potential Vs and the frequency of the incident light, the resulting graph will be a
straight line (Fig.3). The slope of this graph is equal to (h/e) and is the same for
all materials. Millikan showed that the value of h determined from experiments
on the photoelectric effect agrees well with the value obtained from other
experiments.
Thus, the photoelectric effect confirmed the existence of energy in the
form of discrete quanta.

Features of the photoelectric effect.

(i) A photoelectron is emitted from the metal only if the energy of the
incident photon .
(ii) If , electrons not ejected from the metal surface. however
intense, the incident light may be.
(iii) The minimum energy that a photon should have to dislodge an
electron from the metal, without Imparting it any kinetic energy (K.E. = 0), is
given, by .
 Fig 1.8 Potential Vs versus
the frequency of the incident
light
(iv)
Photoelectric effect can
occur only, when the frequency of the incident light is equal to or greater than the
minimum value of threshold frequency n0.
………….(2)
(v) The ejected electrons from the cathode are decelerated as they travel
toward the anode. The potential difference that stop the electrons reaching the
anode and reduces the current in the circuit to zero is called stopping potential
Vs
Kinetic energy of the most energetic electron is
K.E. max = eVs……….(3)
Using the Eq. (1), (2) and (3), we get
……….(4)
Eq (4) shows that stopping potential and hence the kinetic energy of
photoelectron varies linearly with the frequency of the incident light.
Waves & particles:
Wave:- A wave is nothing but spreading of disturbance in a medium. The
characteristics/properties of waves are 1)Amplitude 2) Time period 3) Frequency 4) Wave-
length 5)Phase 6)Intensity.
Particle:- A particle is a point in space which has mass & occupies space or region. The
characteristics/properties of a particle are 1) Mass 2) velocity 3) Momentum 4) Energy etc.
Matter Waves or de-broglie-waves: The waves associated with a material particle are called
as matter waves.
Difference between matter waves and electro-magnetic waves:-

Matter Wave Electromagnetic waves(Light waves)

1. Matter wave is associated with moving 1. Oscillating charged particle gives rise to
particle or material particle. EM wave.
2. Wavelength of an electromagnetic wave is
2. Wavelength of matter wave is given as
given by
h
𝜆= hc
mv 𝜆=
E
3. Wavelength of an electromagnetic wave
3. Wavelength of matter wave depends
depends upon the energy of the photon.
upon mass of the particle & velocity.

4. It can travel with a velocity greater than 4. It can travel with a velocity equal to the
the velocity of light in vacuum. speed of light in vacuum i.e c = × m/s .
5. Electric field and Magnetic field oscillate
5. It is not a EM wave. perpendicular to each other & generate EM
Waves.

de-broglie concept of dual nature of matter waves:-

In 1924 ,Louis de-broglie suggested that matter waves also exhibit dual nature like
radiation(light). They are
I. Wave nature
II. Particle nature
Wave nature of matter waves is verified by Davisson & Germer experiment, G.P.Thomson
experiment etc.
Particle nature of matter waves is verified by photo-electric effect, Compton effect etc.
de-broglie hypothesis:-
1) The universe consists of matter and radiation(light) only
2) Matter waves also exhibit dual nature like radiation.
3) The waves associated with the material particles are called as debroglie-waves or
matter waves & the wave length associated with matter waves are called as de-broglie
wave-length or matter wave-length (λ).
ℎ ℎ
4) de-broglie wave-length is given by 𝜆 = 𝑝 = 𝑣
Expression for de-broglie wave-length(λ) in various form:-
According to the planck’s theory of radiation, the energy of photon is given by
ℎ𝑐
𝐸 = ℎ𝜈 = ----(1)
𝜆
h- planck’s constant, ν-frequency of photon
According to Einstein mass energy relation
E = mc2-----(2)
m-mass of a photon
c-velocity of light
From equation of (1) & (2)
ℎ𝑐
= mc2
𝜆
ℎ ℎ
𝜆= = −−−
𝑣 𝑝
Where p-momentum of of photon = mc
m-mass of photon, c-speed of light
But according to de-broglie theory
Momentum of electron particle(p) = mv
m-mass of e’s , v-velocity of electron particle
ℎ ℎ
de-broglie wave-length(λ) =𝜆 = = 𝑝------(4)
𝑣
Eq.(4) gives the expression for de-broglie wave-length.
Other forms of de-broglie wavelength(λ):-
(i)In terms of Energy(E):-
we know that the kinetic energy of particle i.e. 𝐸 = 𝑣 −−−
Multiply Eq-(5) by ‘m’ on both sides, we get
mE = 𝑣
2 2
2Em = m v
mv = √2mE
ℎ
𝜆=√ ---(6)
𝐸
(ii) de-broglie wavelength in terms of voltage(V):-
If a charged particle is accelerated through a potential difference(V), then the kinetic energy
of the particle is given as
E = eV---(7)
But we have kinetic energy(E) of particle i.e. E = 𝑣
eV = 𝑣
2eV = mv2
Multiply by ‘m’ on both sides we get
2meV = 𝑣 => mv = √ 𝑣
 −
h = 6.6× J-S
ℎ ℎ .
We have de-broglie wavelength 𝜆 = = or 𝜆 = 𝐴°
v √ 𝑒𝑣 √𝑉
h = 6.625× − Js
−
𝑒 = . × 𝑔
−
e = 1.6 ×
(iii) de-broglie wavelength in terms of Temperature(T):-
According to the kinetic theory of gases, the average kinetic energy of a particle at
temperature ‘T’ is given by
E = k𝐵
ℎ ℎ ℎ
𝜆= = =
√ 𝐸 √ × k𝐵 √ k𝐵
k 𝐵 is the Boltzmann constant.
Properties or characteristics of matter waves or de-broglie waves:-
 Lesser the mass of the particle, greater is the wavelength associated with it.
 Smaller the velocity of the particle, longer is the wav-length associated with the
particle.
 When V = 0, 𝜆 = ∞ & 𝑉 = ∞, 𝜆 = .
 Matter waves produced when the particles in motion are charged or uncharged.
 Matter wave are not electro-magnetic waves.
 Matter waves travel faster than the velocity of light.
 Wave nature of matter gives an uncertainty in the position of the particle.
Experimental Verification of matter waves:-
Here, we have two methods to verify the dual nature of matter waves. They are
1. Davisson and Germer’s experiment
2. G.P. Thomson’s experiment
1. Davisson and Germer’s experiment:-
First practical evidence for the wave nature of matter waves was given by C.J.Davisson
and L.H. Germer in 1927. This was the first experimental support to debroglie’s
hypothesis.
Principle: The e’s which are coming from the source are incident on the target and the e’s
get diffracted. These diffracted e’s produce a diffraction pattern. It shows(explains)the
wave nature of matter waves.
Experimental Arrangement:-
Construction:
The experimental setup is shown in above figure. It consists of mainly 3-parts
(i)Filament
(ii)Target
(iii)Circular scale arrangement.
It also consists of a low tension battery(LTB), High tension battery(HTB) & a cylinder(A).
Working:
When tungsten filament ‘F’ is heated by a LTB then e’s are produced. These e’s are
accelerated by High voltage(HTB). The accelerated e’s are collimated into a fine beam of
pencil by passing them through a system of pin-holes in the cylinder ’A’. This beam of
electrons is allowed to incident on nickel crystal which acts as target. Then e’s are scattered
in all the directions. The intensity of scattered e’s is measured by the circular scale
arrangement. In this arrangement, an electron or movable collector(Double walled faraday
cylinder) is fixed to circular scale which can collect the electrons and can move along the
circular scale. The electron collector(Double walled faraday cylinder) is connected to a
sensitive galvanometer to measure the intensity of electron beam entering the collector at
different scattering angles(∅).
A graph is plotted between the scattering angle( ∅) and the number of scattered
electron’s as shown in above figure.
The intensity of scattered e’s is maximum at ∅ = ° & accelerating voltage =54V.

Calculation of wave-length associated with e’s:

2dsin 𝜃 = 𝜆---(1)
For nickel crystal, d = 0. 909𝐴° = . × − m
n = 1, First order
(i)Angle of diffraction(𝜽 𝐏𝐫𝐚𝐜 𝐢𝐜𝐚𝐥 𝐚𝐥 :
From the the figure,
°
=𝜃+𝜃+ °
°
= 𝜃+ °
∴ Diffraction angle( 𝜃 = °----(2)
Substituting the above values in eq − we get
°
2× . × 𝑖 = 1×𝜆
𝜆 = . 𝐴° ---(3)
 𝐢𝐢 From de-broglie wave length(𝝀 :
.
λ= A°
√V
But V = 54v
.
λ= A° = . A°
√
λ = . A° ----(4)
From eq-(3) & eq-(4) it was been proved both the practical & theoretical wavelengths
are almost equal. Hence the wave nature of particle is prove d experimentally.

Heisenberg uncertainty principle:-

The discovery of dual nature of material particle imposes a serious hurdle in locating
the exact position and momentum of a particle simultaneously.
This wax was removed by “Werner. Heisenberg” in 1927 by proposing a significant
principle. Later it was called Heisenberg’s uncertainty principle or Heisenberg’s principle of
indeterminacy.
“It is impossible to measure both the position and momentum of a particle simultaneously to
any desired degree of accuracy.” If ′∆x′ & ′∆p′ are uncertainties in the measurement of
position & momentum of the particle then mathematically this uncertainties of this physical
variables is written as
∆x. ∆p -----(1)
π
Similarly the uncertainties in measuring energy and time interval we can write
(i) ∆E. ∆t and the uncertainties in measuring angular momentum &
π
angular displacement as
(ii) ∆J. ∆θ π
Explanation:-
(i)If ∆x = . i.e., the position of a particle is measured accurately, then from eq-(1).
ℎ
∆p = ∆ . π
ℎ
∆p = = ∞
It means that, the momentum of the particle can’t be measured.
(ii)If ∆p = . i. e. , the momentum of a particle is measured accurately, from eq. .
∆x = ∆p. = =∞
π
From the above said observations made by Heisenberg, he clearly states that it is impossible
to design an experiment to prove the wave & particle nature of matter at any given instant of
time.
If one measures position or momentum accurately, then there will be an uncertainty in the
other.Thus, the Heisenberg’s uncertainty principle gives the probability of determining the
particle at any given instant of time in place of certainty.
Applications:-
(i).It explains the non-existence of e’s in the nucleus.
(ii).It gives the binding energy of an e’s in atom.
(iii).It calculates the radius of Bohr’s first orbit.
Schrodinger Wave Equation:-
Schrodinger describes the wave nature of a particle in mathematical form and is known as
Schrodinger wave equation(SWE). There are two types of SWE
(i). Schrodinger Time independent wave equation(STIWE)
(ii). Schrodinger Time dependent wave equation(STDWE)
(i) Schrodinger Time independent wave equation(STIWE):-
To derive an expression for “(STIWE)” let us consider an electron (particle)moving along a
positive direction along the axes . Let x, y, z be the coordinates of the particle & ′ψ′ is the
wave-displacement or wave-function of the matter wave at any time ’t’. It is assumed that ′ψ′
is finite, single-valued, continuous and periodic function.
We can express the classical differential wave equation of the material particle in three-
dimension axes is given as
∂2 ∂2 ∂2 ∂2
= v +∂ +∂
∂t2 ∂ 2 2 2

∂2
In Three dimension we write =V ∇ −−−
∂t2
The solution of eq-(1) is given by
= sin t − − −
= sin πυt − − −
Where = πυ is the angular frequency of the particle
Differentiating eq-(3) w.r.t. ‘t’ twice we get
∂
= × cos πυt × πυ
∂t

=− × sin πυt × πυ × πυ
𝑡
∂2
= − π ϑ ---(3)
∂t2
c v
ϑ= =
λ λ
∂2 π2 v2
= − ---(4)
∂t 2 λ2
Substituting eq-(4) in eq-(1), we get,
π v ψ
V ∇ ψ=−
λ
𝜋2
∇ + = −−−
𝜆2
According to de-broglie wave-length
 𝜆=p= ---(6)
v
Sub. eq(6) in eq(5), we get
𝜋2 2𝑣2
∇ + = −−−
ℎ2
We have, the total energy (E) is given by
E = P.E. + K.E.
E = V + mv
mv = E − V
mv = E − V
m v = m E−V −−−
Sub. eq-(8) in eq-(7) we get,
𝜋
∇ + m E−V =
ℎ
𝜋 E−V
∇ + = −−−
ℎ
𝐸−𝑉 ℎ
∇ + = −−− Where ℏ =
ℏ2 𝜋
Eq-(9) & Eq-(10) is called as Schrodinger time independent wave equation in three
dimension
For a free particle, V= 0 ,
𝐸
∇ + = −−−
ℏ
(ii)Schrödinger Time dependent wave equation:-
ℏ2
̂H = ̂
E where ̂H = − ∇ + V = Hamiltonian operator
̂ = iℏ ∂ = Energy operator
E ∂t
Physical significance of wave-function(𝛙 𝐄𝐢 − 𝐜𝐢 :−
Wave-function(𝛙 or Eigen-function(𝛙 :-
It is a variable or complex quantity that is associated with a moving particle at any
position (x,y,z) and at any time ‘t’.
(i) ‘ ′ of a particle is represented by = e− t
(ii) ‘ ′ explains the motion of microscopic particles.
(iii) ‘ ′ is a complex quantity & it does not have any meaning.
∗
(iv) | | = is real and positive, it has physical meaning.
(v) | | represents the probability of finding the particle per unit volume.
(vi) For a given volume d τ, the probability of finding the particle is given by
probability density(p) = ∭ |ψ| dτ where dτ = dxdydz
(vii) ‘ ′ gives the information about the particle behavior.
(viii) ‘p’ values are between 0 to 1.
(xi) wave-function ‘ ′ is a single valued, finite and periodic function.
(x) If p = ∭ |ψ| dτ = 1, then ‘ ′ is called normalized wave function.
Application of Schrödinger Time independent wave equation(STIWE):-

(1) Particle or electron in a one dimensional box or particle in an infinite square well
potential:-
Consider a particle or electron of mass ’m’ moving along x-axis enclosed in a one
dimensional potential box as shown in figure. Since the walls are of infinite potential the
particle does not penetrate out from the box. i.e. potential energy of the particle V=∞ at
the walls.
The particle is free to move between the walls A & B at x=0 and x=L.
The potential energy of the particle between the walls is constant because no force is
acting on the particle.
∴ The particle energy is taken as zero for simplicity
𝑖. . V= 0 between x=0 & x=L.
Boundary Conditions:-
(i)The potential energy for particle is given as
V(x) = 0, for 0 𝑥
--------- (1)
V(x) =∞, when 0 𝑥
The Schrödinger time independent wave equation for the
particle is given by,
d π m
+ E−V =
dx h
But v=0, between walls,
d2 π2
2 + 2 E = ----( 2 )
d
π2
Let 2 E =k
Then eq-(2), becomes

+k ψ = −−−
𝑥
The general solution of eq-(3) is given by
𝑥 = Asinkx + Bcoskx------(4)
Where A, B are two constants, ‘k’ is the wave-vector
Applying the boundary conditions eq-(4), we get
(i) = 𝑎𝑡 𝑥 =
0 = Asink(0) + Bcosk(0)
0 = 0 +B
B=0
Then eq-(4) is written as
𝑥 = Asinkx or ψ x = Asin kx ----(6)
(ii) = 𝑎𝑡 𝑥 =
Eq-(6) can be written as
0 =ASin(kL) => A≠ , and sin(kL) = 0
sin(kL) = sin(n𝜋)
𝜋
kL = n𝜋 => k = -----(7)
𝐿
1) Energy of the particle(Electron):-
𝜋 2 2
k= => k =
𝐿 L2
π2
But we have, 2 E =k
2𝜋2 π2
= E
ℎ2 2
2ℎ 2 2ℎ 2
E= => 𝐸 = −−−
𝐿2 𝐿2
(ii)Energy levels of an particle(Electron):-
2
when n=1, 𝐸 = L2
ℎ2
when n=2, 𝐸 = = 𝐸
𝐿2
In general, 𝐸 = 𝐸
∴ Energy levels of an electron are discrete.
(iii) Normalization of the wave-function of the particle to find ‘A’:-
To find the ‘A’ value, by applying the normalization conditions.
𝐿
∫| 𝑥 | 𝑥=
𝐿 𝜋𝑥
∫ 𝐴 𝑖 𝐿
𝑥=
𝐿
𝜋𝑥
𝐴 ∫ 𝑖 𝑥=

By integrating and applying the appropriate limits , finally we obtain the value of ‘A” as

A =√L ----(9)
(iv) Electron wave functions ,probability density functions and energy functions:-
(i) Wave function of electron/particle
𝜋𝑥
x = √L sin 𝐿
-----(10)
(ii) Probability density function(P)
𝜋𝑥
P=| 𝑥 | =L 𝑖 -----(11)
𝐿
(iii)Energy function of the particle
2 ℎ2
𝐸 = ----(12)
𝐿2
 UNIT I: QUANTUM PhYSICS AND SOLIDS

1.1 SYMMETRY ELEMENT OF A CRYSTALLINE SOLID

There are three main symmetry elements used to describe a crystalline solid.
(i) Axis of symmetry
(ii) Plane of symmetry
(iii) Centre of symmetry

1.1.1 Axis of Symmetry

During the rotation of a crystal around an axis, if it occupies two or more identical positions in a
complete rotation (i.e., 360°), then that axis is called the axis of symmetry.
When a cube is rotated around the axis passing through its opposite faces, then each rotation of
90° repeats the identical or congruent position, i.e., four congruent positions in one complete rota-
tion. It is known as a four-fold axis of symmetry. In general, if in a crystal n, the identical positions are repeated
around an axis in one complete rotation, then that axis is called an n-fold axis of symmetry.
There are 13 axes of symmetry for a cube, which are as follows:
(i) 3 axes have four-fold symmetry known as tetrad. These axes pass through opposite face centres as
shown in Fig. 1.1 (a).
(ii) 4 axes have three-fold symmetry known as triad. These axes pass through diagonally opposite comers
as shown in Fig. 1.1 (b).
(iii) 6 axes have two-fold symmetry known as diad. These axes pass through the centres of opposite edges
as shown in Fig. 1.1 (c).

Fig. 1.1 (a) 4-fold axes of symmetry, (b) 3-fold axes of symmetry, and (c) 2-fold axes of symmetry

1.1.2 Planes of Symmetry

If a plane is able to cut a crystal into two halves in such a way that one half becomes the mirror
image of the other half, then that plane is known as the plane of symmetry. There are 9 planes—3
are parallel to the face of the cube [Fig. 1.2(a)] and 6 are diagonal planes passing through diagonally
opposite parallel edges [Fig. 1.2(b)].
 2 Engineering Physics

Fig. 1.2 (a) Parallel plane of symmetry and (b) diagonal plane of symmetry

1.1.3 Centre of Symmetry

The centre of symmetry is defined as a point in a crystal such that if a line is drawn from any point on
the crystal through this point and an equal distance is produced on the other side of this central point,
then it meets an identical point. There is only one centre of symmetry for a cubic system (Fig. 1.3).

Fig. 1.3 (a) Coordinates of corner lattice points, (b) coordinates of body-centred lattice points, and
(c) coordinates of face-centred lattice points

Fig. 1.4 Centre of symmetry in a cubic system

 UNIT I – FREE ELECTRON THEORY & BAND THEORY OF SOLIDS

FREE ELECTRON 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 non metals. 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 first theory was developed 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.

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.

3. Zone Theory: Bloch introduced the band theory in 1928. According to this theory,
free electrons move in a periodic potential provided by the lattice. This theory is also
called “Band Theory of Solids”. It gives complete informational study of electrons.

1) What are the assumptions of classical free electron theory?

Classical free electron theory of metals (Drude – Lorentz theory of metals):

Drude and Lorentz proposed this theory in 1900. According to this theory, the metals
containing the free electrons obey the laws of classical mechanics.

Assumptions (or) Salient features in classical free electron theory

1. In metals there are a large number of free electrons moving freely in all possible
directions.
2. These free electrons behave like gas molecules in a container obeying the laws of
kinetic theory of gases.
3. In the absence of field the energy associated with each electron at a temperature T is
given by kT. It is related to kinetic energy as kT= mvth2. Where vth is the thermal
velocity and k is Boltzmann constant.
4. 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.
5. Electron velocities in a metal obey Maxwell-Boltzmann distribution of velocities.
6. The free electrons move in a constant potential field. Hence the potential energy of the
 electrons is constant.
7. 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.

2. What are the merits and demerits of classical free electron theory?
Success or Advantages or Merits classical free electron theory
1) It verifies ohm’s law.
2) It explains electrical and thermal conductivities of metals.
3) It derives Widemann-Franz law.
4) It explains optical properties of metals.
Limitations or drawbacks or Demerits classical free electron theory
1) It fails to explain the electrical conductivity of semiconductors and insulators.
2) It fails to explain the temperature variation of electrical conductivity at low
temperature.
3) It fails to explain the concept of specific heat of metals.
4) It fails to explain the mean free path of the electrons.
5) The phenomenon like photo electric effect, Compton effect and black body radiation
could not be explained by classical free electron theory.
6) It fails to explain temperature dependence of paramagnetic susceptibility and
ferromagnetism.

3) What are the assumptions of quantum free electron theory?

Quantum Free Electron Theory:
Quantum free electron theory was proposed by Sommerfeld in 1928. It overcomes many
of the drawbacks of classical theory. Sommerfeld explained them by choosing Fermi-
Dirac statistics instead of Maxwell-Boltzmann statistics. He developed this theory by
applying the principles of quantum mechanics.
Assumptions of Quantum Free Electron Theory
1) 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.
2) The distribution of electrons in various allowed energy levels occurs as per Pauli
Exclusion Principle.
3) The attraction between the free electrons and lattice ions and the repulsion between
electrons themselves are ignored.
4) The distribution of energy among the free electrons is according to Fermi-Dirac
statistics.
5) The energy values of free electrons are quantized.
6) 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.
Energy of electron is = , Where n=1, 2, 3,…

3. What are the merits and demerits of quantum free electron theory?
Merits of quantum free electron theory
1. It successfully explains the electrical and thermal conductivity of metals.
2. It can explain the Thermionic phenomenon.
3. It explains temperature dependence of conductivity of metals.
4. It can explain the specific heat of metals.
5. It explains magnetic susceptibility of metals.
6. It can explain photo electric effect, Compton Effect and block body radiation etc.
7. It gives the correct mathematical expression for the thermal conductivity of metals.

Demerits of quantum free electron theory

1. It is unable to explain the metallic properties exhibited by only certain crystals.
2. It is unable to explain why the atomic arrays in metallic crystals should prefer certain
structures only.
3. This theory fails to distinguish between metal, semiconductor and Insulator.
4. It also fails to explain the positive value of Hall Co-efficient.
5. According to this theory, only two electrons are present in the Fermi level and they
are responsible for conduction which is not true.
4. Explain Fermi-Dirac distribution function.

Fermi Dirac Distribution:

A metal piece contains very large number of electrons. Each electron possesses
quantized energy states and obeys Pauli’s exclusion principle. Hence they satisfy Fermi-
Dirac statistics. The probability F(E) of an electron occupying energy level Ei is given by

Where F(Ei) is called Fermi function which is defined as the probability of electron
occupation in the given energy state (Ei) at thermal equilibrium. Ef is Fermi energy, Ei is
energy of ith state and k is Boltzmann constant.

The plot of F(E) Vs E is as shown in fig.

Conclusions: At T=OK, the Fermi Dirac distribution of electrons can be understood

mathematically from the following two cases.
( )
Case -1: If E>EF, =∞
Therefore, F(Ei)= 1/∞ then F(Ei)=0. It indicates that energy levels above Fermi level are
empty.
( )
Case -2: If E<EF, =0 then F(Ei)=1. It indicates that energy levels below Fermi
levels are full of electrons. The Fermi level is a boundary energy level which separates
the filled energy state and empty states at 0k. The energy of the highest filled state at 0K
is called Fermi Energy EF and the energy level is known as Fermi Level.

Case-3: At T>0K, if Ei=EF then F(Ei)=1/2. i.e 50%. Therefore Fermi level is the energy
level for which the probability of filled states is 50% at any temperature. If TF is the
Fermi temperature and VF is Fermi velocity corresponding to Fermi energy EF then
EF =kTF => TF = EF /k and VF = (2E /m)
5. Explain the effect of temperature on Fermi-Dirac distribution.
Effect of temperature on Fermi Dirac distribution:

1. At T=OK, the Fermi Dirac distribution of electrons can be understood mathematically

from the following two cases.
( )
Case -1: If E>EF, =∞
Therefore, F(Ei)= 1/∞ then F(Ei)=0. It indicates that energy levels above Fermi level are
empty.
( )
Case -2: If E<EF, =0 then F(Ei)=1. It indicates that energy levels below Fermi
levels are full of electrons.

2. When T>0, F(EF)<1 for Ei<EF

F(Ei)>0 for Ei>EF
F(Ei)= for Ei=EF
As temperature increases more and more electrons jump to the levels above EF leaving
vacancies as shown in the fig.
3. The electrons in the levels above EF and vacancies in the levels below EF are
responsible for conduction in semiconductors.
4. If the temperature is raised further, the resistance of the metals increases due to
decrease of mobility.
5. At T>0K, the Fermi energy level decreases.
6. According to classical theory, all the free electrons below EF gain energy when
temperature is increased. This deviates theoretical and experimental values.
7. According to quantum theory only few electrons below EF gain energy from external
source. Thus theoretical values are closer to the experimental values.
6. Explain Bloch theorem or electrons in a periodic potential.
Electrons in a periodic potential - Bloch theorem:

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 as we have done in the electron
theory, we have to consider the variation of potential inside the metallic crystal with the
periodicity of the lattice as shown fig.

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
+ ( − #)ψ=0 where ђ = h / 2 Π
² ħ
² $
+ ( − #(&))ψ=0 −−−−−(1)
² %

The periodic potential V(x) may be defined by means of the lattice constant ‘a’ as

#(&) = #(& + () --------- (2)

Bloch has shown that the one-dimensional solution of the Schrödinger equation is of the
form.

ψ(x)= e ikx .Uk (&) -----------(3)

In the above equation Uk(&) is called “modulating function”. Because free electron wave is
modulated by Uk(&) 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
Uk(&)= Uk(&+Na) ------------------ (4)
Where ‘a’ is lattice distance.
ik(x+Na)
From equation (3) and (4), we have ψ(x+Na)= e .Uk (& + )()
ikNa ikx
=e .Uk (&) e
ψ(x+Na) = ψ(x). e ikNa ------------------ (5)
This is referred to as Bloch condition. Similarly, the complex conjugate of eq.(5) can be
written as
ψ∗(x+Na) = ψ∗(x). e –ikNa --------------(6)
From eq(5) and eq(6)
ψ(x+Na) . ψ∗(x+Na) = ψ(x). ψ∗(x)

|ψ(x+Na)|2 = |ψ(x)|2 --------(7)

This means that the electron is not localized around ones particular atom and the
probability of finding the electron is same throughout the crystal.

ikNa
Hence in eq(5), e =1

kNa=2Πn , where n is an integer

k=(2Πn)/Na

k=(2Πn)/L

Where L is the length of the chain of atoms and n= ±1, ±2, ±3, ±4, ………
When n=N/2, we have k=Π/a. This is the edge of first Brillouin zone.
7. Explain Kronig-Penny model

Kronig – Penny Model:

Kronig – Penny Model proposed a simpler potential in the form of an array of square
wells as shown in the fig.

Schrodinger equation for one dimensional periodic potential field denoted by V(x) can be
written as

² $
+ ( − #(&))ψ=0 −−−−−(1)
² %
According to Bloch theorem the solutions of this equation have the form

ψ(x)= e ikx .Uk (&) -----------(2)

Where Uk (&) is periodic with the periodicity of the lattice. That is,

Uk (& + () = Uk (&)

As Vo increases the width of the barrier ω decreases so that the product Voω remains
constant. It turns out that solutions are possible only for energies given by the relation

. /01∝3
cos -( = + cos ∝ ( -------------(3)
∝3

4$ 3 $
Where P = Voω and ∝= √28
P is called scattering power of the barrier and Voω is called barrier strength.

The left hand side of the equation (3) is plotted as a function of ‘∝a’ for the value of P
= 3 Π / 2 which is shown in fig, the right hand side takes values between -1 to +1 as
indicated by the horizontal lines in fig. Therefore the equation (3) is satisfied only for
those values of ‘ka’ for which left hand side between ± 1.
From fig , the following conclusions are drawn.
1) The energy spectrum of the electron consists of a number of allowed and forbidden
energy bands.
2) As ‘∝a’ increases the width of the allowed energy band increases and the width of
forbidden band decreases.
3) With increasing potential barrier P, the width of an allowed band decreases.
4) As P→∞, the allowed energy becomes infinitely narrow and the energy spectrum is a
line spectrum as shown in fig.
5) When P→0 then all the electrons are completely free to move in the crystal without
any constraints. Hence, no energy level exists that is all the energies are allowed to the
electrons as shown in fig. This case supports the classical free electrons theory.
8. Explain Brillouin zones with the help of E-K diagram.
Brillouin Zones (E-K curve):
. /01∝3
Using the equation cos -( = + cos ∝ (
∝3
it is possible to plot a curve showing the energy E as a function of K as shown in fig.

$
From fig. it is clear that energy of electron is continuously increasing from K=0 to . The
3
$
left hand side of above equation becomes +1 or -1 for values of K=± and hence
3
$
discontinuity appears in E-K graph, at K=± 3 . From fig it is seen that energy spectrum
of electron consists of allowed regions and forbidden regions. The allowed region extends
$ $
from - to + . This is known as first Brillouin Zone. After a discontinuity in energy
3 3
$ $ $ $
called forbidden gap another allowed region extends from - to - and to . This is
3 3 3 3
known as second Brillouin Zone. Similarly other higher order Brillouin zones can be
defined.
9. Explain the origin of energy bands in crystalline
rystalline solids.
Origin of Energy Bands in Solids:
An isolated atom possesses discrete energies of different electrons. Suppose two isolated
atoms are brought to very close proximity, then the electrons in the orbits of two atoms
interact with each other.
her. So, that in the combined system, the energies of electrons will
not be in the same level but changes and the energies will be slightly lower and larger
than the original value. So, at the place of each energy level, a closely spaced two energy
levels exists. If ‘N’’ number of atoms are brought together to form a solid and if these
atoms’ electrons interact and give ‘N’‘ ’ number of closely spaced energy levels in the place
of discrete energy levels, it is known as bands of allowed energies.

The width of energy band depends on the degree of over lapping of electrons of adjacent
atoms and is largest for outermost electrons. The band corresponding to outer most
orbits is called conduction band and next inner band is called valence band. The gap
between these two allowed bands is called forbidden energy gap or band gap Eg.

10. On the basis of band theory how the crystalline solids are classified into
metals, semiconductors and Insulators.
Insulators

Classification of crystalline solids:

Based on the width of forbidden band, solids are classified into insulators,
Semiconductors and conductors.
Conductors: The valence band and conduction bands are overlapped with each other
and the energy gap Eg is zero. At room temperatures, free electrons already exist in huge
number at conduction band. Hence these solids are good electrical conductors as well as
good thermal conductors. The electrical resistivity increases at high temperature by
collisions among the free electrons.
Ex: Al, Cu, Ag, Au etc.,

Semiconductors: The valence band and conduction bands are separated with a small
energy band gap Eg ≈ 1 eV. At low temperatures (0 K), free electrons are not available in
conduction band. Hence they behave like insulators at low temperatures. The electrical
conductivity increases at high temperatures by the transition of free electrons from
valence band to conduction band. Thus these solids behave like electrical conductors at
high temperatures.
Ex: Silicon Eg = 1.1 ev, Germanium Eg = 0.7ev

Insulators: The valance band and conduction bands are separated by a very large
energy gap Eg ≥ 3 eV. At room temperatures conduction band is empty and valance band
is full of electrons. Hence they these solids are electrical insulators. Even at high
temperatures valence electrons are unable to jump in to conduction band.
Ex: Glass, Mica, Ebonite, Rubber etc.,

14. Explain the effective mass of electron and concept of hole.

Effective mass of the electron:
When an electron in a period potential is accelerated by an electric field (or) magnetic
field, then the mass of the electron is called effective mass ( m*).
Let an electron of charge ‘e’ and mass ‘m’ moving inside a crystal lattice of electric field
E. Acceleration a = eE / m is not a constant in the periodic lattice of the crystal. It can
be considered that its variation is caused by the variation of electron’s mass when it
moves in the crystal lattice.
Therefore Acceleration a = eE / m*
Electrical force on the electron F = m* a --------------(1)

Considering the free electron as a wave packet , the group velocity vg corresponding to
the particle’s velocity can be written as

:; :( $=) := 2Π :( =) :@
vg = = = 2Π =( ) = ---------(2)
:< :< :< h :< ħ :<

where, the energy E = hυ and ħ =

2Π

1D 2
:Vg :( ) 1 D : @ :< : @ :<
Acceleration a = = ħ D-
= ħ D-.DE = ( )( ) = ( )( )
:B :B ħ :<.:< :B ħ :< :B
:. :< F
Since ħk = p and = F, =
:B :B ħ

: @
∴a= ( )F
ħ2 :<
 ħ
F=[ G H
]a ------------(3)
( )
GI

Comparing equations (1) and (3) we get

ħ
m*=[ G H
]---------------(4)
( )
GI

: @
This equation indicates that the effective mass is determined by .
:<

a. Variation of E with K: Variation of E with

K corresponds to first Brillouin Zone. Using
this type of variation velocity can be
calculated.

b. Variation of V with K: For K=0 velocity is

zero and as k value increases V also increases
reaching its maximum value at Ko known as
point of inflexion. Beyond Ko velocity
decreases and reaches to 0 at K=π/a.

c. Variation of m* with K: Near K=0, m*=m.

As K value increases m* also increases
reaching its maximum value at Ko. Above Ko ,
m* is negative and decreases as K tends to
π/a. Beyond Ko velocity decreases and hence
retarding force acts on electron and it
behaves as positively charged particle referred
to as hole.

d. Variation of fk : Degree of freedom of an

electron is defined as fk=m/m*. fk is measure
of the extent to which the electron is free in a
state K. If m* is large fk is small, particle
behaves as heavy particle. If fk=1, electron
behaves as free electron.
 Assignment questions

1. What are the merits and demerits of classical free electron theory?
2. What are the assumptions of quantum free electron theory? What are the merits and
demerits?
3. Derive an expression for electrical conductivity on the basis of quantum free electron
theory.
4. What is Fermi level? Explain the Fermi- Dirac distribution function of electrons.
Illustrate graphically the effect of temperature on the distribution.
5. What is Bloch theorem? Explain.
6. Discuss the Kronig-Penney model for the motion of an electron in a periodic potential.
7. Explain the concept of effective mass of electron and hole.
8. Explain the origin of energy bands in solids. On the basis of band theory how the
crystalline solids are classified into metals, semiconductors and Insulators?

Problems
1. Evaluate the Fermi function for an energy KT above Fermi energy.
2. At what temperature we can expect 10% probability that the electrons in silver have
an energy which is 1% above the Fermi energy. The Fermi energy of silver is 5.5 eV.

3. Calculate the Fermi energy in eV for silver at 0 K. The number of conduction

electrons in silver is 5.863 * 1028/m3

4. Fermi level for potassium is 2.1eV. Calculate the velocity of the electron at Fermi level.

5. In a solid consider the energy level lying 0.01eV below the Fermi level. What is the
probability of this level not being occupied by an electron?
 Online bits

1. Classical free electron theory was developed by

a) Lorentz b) Drude and Lorentz c) Bloch d) Newton
2. Sommerfeld developed
a) Classical free electron theory b) Quantum free electron theory
c) Zone theory d) Band theory
3. The average distance travelled by an electron between two successive collisions is
called
a) Displacement b) Mean free path c) Drift d) Relative displacement
4. Average drift velocity per unit electron field strength is known as
a) RMS Velocity b) Random Velocity c) Mobility d) Conductivity
5. The current density is related to electric field strength is known as
a) j=σE b) j= E/ σ c) j=ρe d) j= ρ/E
6. Random motion of electrons produce
a) Less current b) Maximum current c) No current d) Variable current
7. According to classical theory, electrons obey
a) Bose Einstein statistics b) Maxwell Boltzmann statistics
c) Fermi Dirac statistics d) Planck’s law
8. Electron collisions according to classical theory are
a) Elastic b) Inelastic c) Semi-elastic d) None
9. According to classical theory electrons move in
a) Uniform potential field in the lattice b) Non uniform potential field
c) Periodic potential field d) Sinusoidal potential field
10. Specific heat of metals according to classical theory is
a) 3R b) 4R c) 3.5R d) 4.5R

11. According to Kronig-Penney model the width of the allowed energy band is
a) constant b) increase with increasing αa
c) decrease with increasing αa d) none

12. According to Kronig –Penney model the electron moves under a potential which is in
the form of
a) a train of sinusoidal waves b) a barrier of constant height
c) a stair case d) an array of rectangular wells

13. The mass of an electron varies with variation of

a) electrostatic field b) magnetic field c) gravitational field d) velocity

14. The origin of energy bands is explained by

a) Drude model b) Lorentz model c) Sommerfeld model d) Kronig–Penney model

15. For an electron in a periodic field the potential at the core site is
a) zero b) moderate c) very small d) infinite
16. From the E-K curve at k=0 the velocity of electrons is
a) maximum b) minimum c) zero d) moderate

17. In an allowed band the velocity of electron is zero at

a) top b) bottom and top c) middle d) bottom

18. Band theory of solids is mainly due to

a) overlapping of all the orbits b) overlapping of outermost orbits
c) closely packed atoms d) both b and c

19. At absolute zero the semiconductors have the band structure similar to
a) conductors b) insulators c) semiconductors d) superconductor

20. First Brillouin zone corresponds to k value extending from

$ $ $ 2K $ L L
a) 0 to b) to c) − ( to d) - to
3 3 3 3 M M