Unit-4: QUANTUM MECHANICSAND FREE ELECTRON THEORY

Introduction

The classical theory was developed by Drude and Lorentz in 1900. According
to this theory, the metals containing free electrons obey the laws of classical
mechanics such as electron can roam anywhere in the metal, they obey kinetic
theory of gases and treated as free electron gas. This theory explained successfully,
the motion of macroscopic particles which can be observed either directly or through
microscopes. This theory also explained successfully the phenomena such as ohm’s
law, electrical & thermal conductivities and optical properties but failed in explaining
the phenomena such as Photoelectric Effect, Compton Effect and Black body
radiation. Then the necessity of development of new theory (quantum theory) was
arised.

The quantum theory was developed by Max Plank in the early of 20th century.
In 1928, Summerfield explained the quantum free electron theory with the help of
laws of quantum mechanics such as electrons move only in the stationary orbital and
their motion is conditional. As per this theory Einstein could be explained the
phenomenon of Photoelectric Effect and proved that light exhibits dual nature. Hence
it is proved that light exhibits dual nature and which motivated towards the existence
of matter waves. Though quantum theory explained several phenomena, it is failed
in explaining the classification of solid into metals, semiconductors and insulators
therefore; the necessity of new theory was arised again to explain this phenomenon
(Band theory of solids).

The band theory of solids was developed by Bloch in 1928. According to this
theory, the free electrons move in a periodic potential proved by the crystal lattice.
This theory successfully explained the phenomenon of classification of metals,
semiconductors and insulators.

Matter waves

If a certain amount of quantity occupies a certain space then it becomes a

particle. The particle has mass. As it is occupying a certain space, its position can be
identified. When its position changes then it has velocity. Due to its mass and
velocity, the particle has momentum and energy. From all these items it is clear that
the characteristic of a particle are mass, velocity, momentum and energy.

A wave is nothing but spreading of disturbance in a medium. Thus the

characteristics of waves are amplitude, time period, frequency, wavelength, phase
and intensity.

To explain the phenomenon which involves both particle and wave nature, we
use Plank’s quantum theory. According to the quantum theory, the emission of
radiation will be in the form of photons. A photon has a velocity of light and mass in
motion. Thus, it has momentum and energy. That means a photon behaves as a

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 Unit-4: QUANTUM MECHANICSAND FREE ELECTRON THEORY

particle. The energy of a photon is given by E = h𝜗𝜗 where 𝜗𝜗 is the frequency of

radiation. Along with frequency, other parameters attribute a wave nature to photon.
This concept of dual nature of radiation prompted de Broglie to suggest the idea of
matter waves.

de Broglie hypothesis

The dual nature of light possessing both wave and particle properties was
explained by combining Plank’s expression for the energy of a photon E = h𝜗𝜗 with
Einstein’s mass energy relation E = mc2 (where c is velocity of light , h is Plank’s
constant , m is mass of particle )

h𝜗𝜗 = mc2

Introducing 𝜗𝜗 = c / λ, we get hc / λ = mc2

==> λ = h / mc = h / p where p is momentum of particle

λ is de Broglie wavelength associated with a photon.

de Broglie proposed the concept of matter waves , according to which a

material particle of mass ‘m’ moving with velocity ‘v’ should be associated with de
Broglie wavelength ‘λ’ given by

λ = h / mv = h / p

The above eqn represents de Broglie wave eqn.

de Broglie wavelength in terms of KE

The KE of a moving particle E = (1/2) mv2

1 p2
= m2 v2 = < ∵ p = mv >
2m 2m

P = √2mE

ℎ
∴ 𝜆𝜆 =
√2mE

de Broglie wavelength of Electrons

Let us consider that an electron of mass m and charge e is accelerated

through a potential difference of Frequency volts. The energy acquired by the
electron is eV and is related to ½ mv2, i.e.,

(½) mv2 = eV or mv2 = 2eV

m2 v2 = 2meV

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 Unit-4: QUANTUM MECHANICSAND FREE ELECTRON THEORY

mv = √2meV

ℎ
∴ 𝜆𝜆 =
√2meV

Substituting the values of h, m, and e in the above eqn, we get

12.26
𝜆𝜆 = Å
√V

Properties of de Broglie waves

Since λ = h / m v

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

2. Lesser the velocity of the particle, longer the wavelength associated with it.

3. For v = 0, λ = ∞. This means that only with moving particle, matter waves is
associated.

4. Whether the particle is changed or not, matter waves is associated with it.

5. It can be proved that matter waves travel faster than light.

6. No single phenomena exhibit both particle nature and wave nature

simultaneously.

7. The wave nature of matter introduces an uncertainty in the location of the particle
& the momentum of the particle exists when both are determined simultaneously.

Heisenberg Uncertainty Principle

According to classical mechanics, a moving particle at any instant has a fixed

position in space and a definite momentum which can be determined simultaneously
with any desired accuracy. The classical point of view represents an approximation
which is adequate for the objects of appreciable size, but not for the particles of
atomic dimensions.

Since a moving particle has to be regarded as a de Broglie group, there is a

limit to the accuracy with which we can measure the particle properties. The particle
may be found anywhere within the wave group, moving with the group velocity. If the
group is narrow, it is easy to locate its position but the uncertainty in calculating its
velocity or momentum increases. On the other hand, if the group is wide, its
momentum can be estimated satisfactorily, but the uncertainty in finding the location
of the particle is great. Heisenberg stated that the simultaneous determination of
exact position and momentum of a moving particle is impossible.

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 Unit-4: QUANTUM MECHANICSAND FREE ELECTRON THEORY

If Δx is Error in the measurement of position of the particle along X-axis

Δp is Error in the measurement of momentum

Then Δx. Δp = h ---------- (1) where h is Plank’s constant

The above relation represents the uncertainty involved in measurement of

both the position and momentum of the particle.

To optimize the above error, lower limit is applied to the eqn. (1)

Then (Δx)(Δp) ≥ ћ / 2 where ћ = h / 2π

A particle can be exactly located (Δ x → 0) only at the expense of an infinite

momentum (Δ p → ∞).

There are uncertainty relations between position and momentum, energy and
time, and angular momentum and angle.

If the time during which a system occupies a certain state is not greater than
Δt, then the energy of the state cannot be known within ΔE,

i.e., (ΔE)(Δt) ≥ ћ / 2 .

Applications

1) Using uncertainty principle, non-existence of electron in the nucleus can be

proved.
2) Existence of protons, neutrons, and 𝛼𝛼 particles in the nucleons is conformed
by the uncertainty principle.
3) Binding energy of an electron in an atom can be calculated from this
uncertainty principle.
4) Emission of radiation of light from an excited atom is also conformed by this
principle.

Schrödinger’s One-dimensional Time Independent Wave Equation

According to de Broglie hypothesis, the particle in motion is always associated

with a wave. To describe the motion of a particle in terms of its associated wave,
Schrödinger derived a wave equation which is termed as Schrödinger’s wave
equation.

Consider a particle of mass ‘m’ moving with velocity ‘v’ along the x direction. It
is associated with a wave. The displacement of a wave is given by the wave function
Ψ.

Since the wave function depends upon the x coordinate of the moving particle
and time ‘t’, it is given by the complex form

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 Unit-4: QUANTUM MECHANICSAND FREE ELECTRON THEORY

Ψ(x, t) = A𝑒𝑒 𝑖𝑖(𝑘𝑘𝑘𝑘 −𝜔𝜔𝜔𝜔 ) ------------ (1)

where A is amplitude

diff eqn(1) w.r.t, x we get

𝑑𝑑𝑑𝑑
= 𝑖𝑖𝑖𝑖 𝐴𝐴𝑒𝑒 𝑖𝑖(𝑘𝑘𝑘𝑘 −𝜔𝜔𝜔𝜔 )
𝑑𝑑𝑑𝑑

Again diff , we have

𝑑𝑑 2 𝛹𝛹
= 𝑖𝑖 2 𝑘𝑘 2 𝐴𝐴𝑒𝑒 𝑖𝑖(𝑘𝑘𝑘𝑘 −𝜔𝜔𝜔𝜔 )
𝑑𝑑𝑥𝑥 2

= 𝑖𝑖 2 𝑘𝑘 2 Ψ

𝑑𝑑 2 𝛹𝛹
= - k2 Ψ
𝑑𝑑𝑥𝑥 2
2𝜋𝜋
Since k= , we get
𝜆𝜆

𝑑𝑑 2 𝛹𝛹 −4𝜋𝜋 2
= Ψ ------------- (2)
𝑑𝑑𝑥𝑥 2 𝜆𝜆 2

de Broglie wavelength associated with the particle is

ℎ
𝜆𝜆 =
𝑚𝑚𝑚𝑚
1
1 𝑚𝑚 2 𝑣𝑣 2 2𝑚𝑚 ( 𝑚𝑚 𝑣𝑣 2 )
= = 2
------------ (3)
𝜆𝜆 2 ℎ2 ℎ2

Let E be the total energy of the particle and V be the potential energy of the
particle. Then
1
KE = mv2 = E − V
2

Using the above value in eqn(3), we get

1 2𝑚𝑚
= (𝐸𝐸 − 𝑉𝑉)
𝜆𝜆 2 ℎ2

Using the above value in eqn(2), we get

𝑑𝑑 2 𝛹𝛹 −8𝜋𝜋 2 𝑚𝑚
= (𝐸𝐸 − 𝑉𝑉)Ψ
𝑑𝑑𝑥𝑥 2 ℎ2

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 Unit-4: QUANTUM MECHANICSAND FREE ELECTRON THEORY

𝑑𝑑 2 𝛹𝛹 8𝜋𝜋 2 𝑚𝑚
+ (𝐸𝐸 − 𝑉𝑉)Ψ = 0
𝑑𝑑𝑥𝑥 2 ℎ2

𝑑𝑑 2 𝛹𝛹 2𝑚𝑚 ℎ
+ (𝐸𝐸 − 𝑉𝑉)Ψ = 0 ( ∵ ћ = )
𝑑𝑑𝑥𝑥 2 ћ2 2𝜋𝜋

The above equation represents Schrödinger’s one-Dimensional time

independent wave equation. For three dimensional motion of the particle the above
equation becomes
2𝑚𝑚
∇2 𝛹𝛹 + (𝐸𝐸 − 𝑉𝑉 )𝛹𝛹 = 0
ћ2

𝑑𝑑 2 𝑑𝑑 2 𝑑𝑑 2
Where ∇ =2
+ +
𝑑𝑑𝑥𝑥 2 𝑑𝑑𝑦𝑦 2 𝑑𝑑𝑧𝑧 2

Schrödinger’s One-dimensional Time Dependent Wave Equation

Let us eliminate the total energy E from time independent wave equation. The
wave function is given by

Ψ(x, t) = A𝑒𝑒 𝑖𝑖(𝑘𝑘𝑘𝑘 −𝜔𝜔𝜔𝜔 )

Diff the above eqn w.r.t, ‘t’, we get

𝑑𝑑𝑑𝑑
= −𝑖𝑖𝑖𝑖 𝐴𝐴𝑒𝑒 𝑖𝑖(𝑘𝑘𝑘𝑘 −𝜔𝜔𝜔𝜔 )
𝑑𝑑𝑑𝑑

= − 𝑖𝑖 (2𝜋𝜋𝜋𝜋) 𝐴𝐴𝑒𝑒 𝑖𝑖(𝑘𝑘𝑘𝑘 −𝜔𝜔𝜔𝜔 )

= − 2𝜋𝜋𝑖𝑖𝜗𝜗 Ψ

𝐸𝐸
Since E = h𝜗𝜗 , 𝜗𝜗 =
ℎ

𝑑𝑑𝑑𝑑 2𝜋𝜋𝜋𝜋𝜋𝜋
=− 𝛹𝛹
𝑑𝑑𝑑𝑑 ℎ

2𝜋𝜋𝜋𝜋𝜋𝜋
=− 𝛹𝛹 (since h = 2πћ)
2𝜋𝜋ћ
𝑑𝑑𝑑𝑑 𝐸𝐸𝐸𝐸
=
𝑑𝑑𝑑𝑑 𝑖𝑖ћ
𝑑𝑑𝑑𝑑
𝐸𝐸𝐸𝐸 = 𝑖𝑖ћ
𝑑𝑑𝑑𝑑

using the value of 𝐸𝐸𝐸𝐸 in the eqn

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 Unit-4: QUANTUM MECHANICSAND FREE ELECTRON THEORY

𝑑𝑑 2 𝛹𝛹 2𝑚𝑚
+ (𝐸𝐸 − 𝑉𝑉)Ψ = 0
𝑑𝑑𝑥𝑥 2 ћ2

𝑑𝑑 2 𝛹𝛹 2𝑚𝑚 𝑑𝑑𝑑𝑑
We get + �𝑖𝑖ћ 𝑑𝑑𝑑𝑑 − 𝑉𝑉𝑉𝑉� = 0
𝑑𝑑𝑥𝑥 2 ћ2

𝑑𝑑 2 𝛹𝛹 2𝑚𝑚 𝑑𝑑𝑑𝑑
=− 2 �𝑖𝑖ћ − 𝑉𝑉𝑉𝑉�
𝑑𝑑𝑥𝑥 2 ћ 𝑑𝑑𝑑𝑑

−ћ2 𝑑𝑑 2 𝛹𝛹 𝑑𝑑𝑑𝑑
+ 𝑉𝑉𝑉𝑉 = 𝑖𝑖ћ
2𝑚𝑚 𝑑𝑑𝑥𝑥 2 𝑑𝑑𝑑𝑑

The above equation represents time dependent Schrödinger’s one-

dimensional wave equation. For three dimensional motions, the above equation
becomes

−ћ2 𝑑𝑑𝑑𝑑
∇2 𝛹𝛹 + 𝑉𝑉𝑉𝑉 = 𝑖𝑖ћ
2𝑚𝑚 𝑑𝑑𝑑𝑑

Physical significance of wave function Ψ

Max Born in 1926 gave a satisfactory interpretation of the wave function Ψ

associated with a moving particle. He postulated that the square of the magnitude of
the wave function |Ψ|2 (or ΨΨ* it Ψ is complex), evaluated at a particular point
represents the probability of finding the particle at the point. |Ψ|2 is called the
probability density and Ψ is the probability amplitude. Thus the probability of the
particle within an element volume dt is |Ψ|2 d 𝜏𝜏 . Since the particle is certainly
somewhere, the integral at |Ψ|2 d𝜏𝜏 over all space must be unity i.e.
∞
∫−∞ |Ψ|2 dτ = 1

A wave function that obeys the above equations is said to be normalized.

Energy acceptable wave function must be normalizable besides being normalizable;
an acceptable wave function should fulfill the following requirements (limitations)

1. It must be finite everywhere.

2. It must be single valued.

3. It must be continuous and have a continuous first derivative everywhere.

Particle in a one dimensional infinite potential well

Consider a particle of mass m moving back and forth between the walls of a
one dimensional box separated by a distance ‘a’ as shown in fig. Let the particle
travel only along the x-axis and is confined between x = 0 and x = a by two infinitely
hard walls so that the particle has no chance of penetrating them.

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 Unit-4: QUANTUM MECHANICSAND FREE ELECTRON THEORY

Thus, it does not lose energy when it collides the walls and its total remains
constant. This box can be represented by a potential box of width a with potential
walls of infinite height at x = 0 and x = a so that the potential energy, V of the particle
is infinitely high on both sides of the box and inside it, Frequency is uniform. Let us
assume that V = 0 inside the box,

V(x) = 0, for 0 < x < a,

V(x) = ∞, for x ≤ 0 and x ≥ a.

Then the wave function Ψ(x) of the particle in the region 0 < x < a where V = 0
is described by the Schrödinger’s equation

𝑑𝑑 2 𝛹𝛹 2𝑚𝑚
+ � 2 � 𝐸𝐸𝐸𝐸 = 0
𝑑𝑑𝑥𝑥 2 ћ

𝑑𝑑 2 𝛹𝛹 2𝑚𝑚𝑚𝑚
+ 𝑘𝑘 2 𝛹𝛹 = 0 Where 𝑘𝑘 = �
𝑑𝑑𝑥𝑥 2 ћ2

The solution of the above equation is given by

𝛹𝛹 (𝑥𝑥) = 𝐴𝐴 sin 𝐾𝐾𝐾𝐾 + 𝐵𝐵 cos 𝐾𝐾𝐾𝐾

Where A and B are arbitrary constants.

Applying the first boundary condition, i.e., at x = 0, 𝛹𝛹(𝑥𝑥) = 0, we get

B=0

Applying the second boundary condition, we have at x = a, 𝛹𝛹(𝑥𝑥) = 𝛹𝛹(𝑎𝑎) = 0

𝛹𝛹 (𝑎𝑎) = 𝐴𝐴 sin 𝐾𝐾𝐾𝐾 = 0

A ≠ 0 since there will not be any solution. Hence we have

sin 𝐾𝐾𝐾𝐾 = 0
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 Unit-4: QUANTUM MECHANICSAND FREE ELECTRON THEORY

𝐾𝐾𝐾𝐾 = nπ
𝑛𝑛𝑛𝑛
𝑘𝑘 = Where n = 1,2,3,…….
𝑎𝑎

We cannot take n =0 because for n = 0, K = 0, E = 0 and hence 𝛹𝛹(𝑥𝑥) = 0

everywhere in the box. Thus a particle with zero energy cannot be present in the
box. The wave function for the motion of the particle in the region 0 < x < a are given
by

𝛹𝛹𝑛𝑛 (𝑥𝑥) = 𝐴𝐴 sin 𝐾𝐾𝐾𝐾

𝑛𝑛𝑛𝑛𝑛𝑛
𝛹𝛹𝑛𝑛 (𝑥𝑥) = 𝐴𝐴 sin
𝑎𝑎

Eigen values of Energy

2𝑚𝑚𝑚𝑚
We know that 𝐾𝐾 2 =
ћ2

𝐾𝐾 2 ћ2
𝐸𝐸 =
2𝑚𝑚

Using the values of K, we get

𝑛𝑛 2 𝜋𝜋 2 ћ2
𝐸𝐸 = [ ]
𝑎𝑎 2 2𝑚𝑚

𝑛𝑛 2 𝜋𝜋 2 ℎ2
= [ ]
𝑎𝑎 2 8𝜋𝜋 2 𝑚𝑚

𝑛𝑛 2 ℎ 2
𝐸𝐸𝑛𝑛 =
8𝑚𝑚 𝑎𝑎 2

From the above eqn, it is clear that

1. The lowest energy of the particle is obtained by putting n = 1

ℎ2
𝐸𝐸1 = and 𝐸𝐸𝑛𝑛 = 𝑛𝑛2 𝐸𝐸1
8𝑚𝑚 𝑎𝑎 2

This is known as zero point energy of the system.

2. For n = 1,2,3, we get discrete energy values of the particle in the box.

ℎ2
𝐸𝐸1 =
8𝑚𝑚 𝑎𝑎 2

ℎ2
𝐸𝐸2 = 22 = 4𝐸𝐸1
8𝑚𝑚 𝑎𝑎 2
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 Unit-4: QUANTUM MECHANICSAND FREE ELECTRON THEORY

2 ℎ2
𝐸𝐸3 = 3 = 9𝐸𝐸1
8𝑚𝑚 𝑎𝑎 2

3. The spacing between the nth energy level and the next higher level increases
as

(𝑛𝑛 + 1)2 𝐸𝐸1 − 𝑛𝑛2 𝐸𝐸1 = (2𝑛𝑛 + 1)𝐸𝐸1

4. These values of E n are known as Eigen values of energy and the

corresponding wave function Ψ n as Eigen functions of the particle. Fig shows
the energy level diagram for the particle.

Eigen Wave Function

The eigenwave function for the motion of the particle are

𝑛𝑛𝑛𝑛𝑛𝑛
𝛹𝛹𝑛𝑛 (𝑥𝑥) = 𝐴𝐴 sin in the region 0<x<a
𝑎𝑎

𝛹𝛹𝑛𝑛 (𝑥𝑥) = 0 in the region 𝑥𝑥 ≤ 0 𝑎𝑎𝑎𝑎𝑎𝑎 𝑥𝑥 ≥ 𝑎𝑎

The total probability that the particle is somewhere in the box must be unity.
𝑎𝑎 𝑎𝑎
∫0 𝑃𝑃𝑥𝑥 𝑑𝑑𝑑𝑑 = ∫0 |𝛹𝛹𝑛𝑛 |2 𝑑𝑑𝑑𝑑 = 1
𝑎𝑎 𝑛𝑛𝑛𝑛𝑛𝑛
∫0 𝐴𝐴2 𝑠𝑠𝑠𝑠𝑠𝑠2 𝑎𝑎
𝑑𝑑𝑑𝑑 = 1

𝐴𝐴2 𝑎𝑎 2𝑛𝑛𝑛𝑛𝑛𝑛
2
∫0 [1 − cos 𝑎𝑎
]𝑑𝑑𝑑𝑑 = 1

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 Unit-4: QUANTUM MECHANICSAND FREE ELECTRON THEORY

𝐴𝐴2 𝑎𝑎 2𝜋𝜋𝜋𝜋𝜋𝜋 𝑎𝑎
�𝑥𝑥 − sin � =1
2 2𝜋𝜋𝜋𝜋 𝑎𝑎 0

The second term becomes zero at both the limits

𝐴𝐴2 𝑎𝑎
=1
2

2
𝐴𝐴 = �
𝑎𝑎

The normalized wave function is

2 𝑛𝑛𝑛𝑛𝑛𝑛
𝛹𝛹𝑛𝑛 (𝑥𝑥) = � sin
𝑎𝑎 𝑎𝑎

The wave functions are shown in fig.

The wave function 𝛹𝛹1 has two nodes at x = 0 and x = a.

𝛹𝛹2 has three nodes at x = 0, x = a/2 and x = a.

Thus 𝛹𝛹𝑛𝑛 has (n+1) nodes.

11
 Free Electron Theory
Introduction:
In solids, electrons in outer most orbits of atoms determine its electrical properties. Electron
theory explains the electrical, thermal and magnetic properties of solids, particularly metals.The
electron theory of solids aredeveloped in three main stages.
1. Classical free electron theory.
2. Quantum Free Electron Theory.
3. Zone Theory/Band Theory.

Classical free electron theory: It was developed by Drude and Lorentz in 1900. According to
this theory, metal contains free electrons which are responsible for the electrical conductivity.
These free electrons obey the laws of classical mechanics.
Postulates (or) Salient features in classical free electron theory
 The valence electrons of metallic atoms are free to move about the whole volume of the
metals like the molecules of a gas in a container. The collection of valence electrons from
all the atoms in a given piece of metal forms electron gas. It is free to move throughout
the volume of the metal.
 These free electrons move in random directions and make collisions with either positive
ions fixed in the lattice or other free electrons. All the collisions are elastic i.e., there is no
loss of energy.
 The movements of free electrons obey the laws of the classical kinetic theory of gases.
 The velocities of free electrons in a metal obey the classical Maxwell-Boltzmann law of
distribution of velocities.
 The free electrons move in a completely uniform potential field due to ions fixed in the
lattice.
 When an electric field is applied to the metal, the free electrons are accelerated in the
direction opposite to the direction of applied electric field (towards positive terminal of
the source). The average velocity acquired by an electron in the presence of electric field
is known as ‘drift velocity (v d ).
 In the absence of the electric field, the distance traveled between two successive
collisions is called mean free path (λ) and the time taken by an electron between two
successive collisions is known as relaxation time (τ). The average velocity of free
electrons is called ‘root mean square velocity, (v rms ) or thermal velocity of electrons.
Success of classical free electron theory: It was only able to explain the properties of metals
such as
 Electrical conductivity.
 Ohm’s law.
 Thermal conductivity.
 Wiedemann-Franz law.
 Complete opacity of metals and their high luster.
Failure of classical free electron theory
 It could not explained the difference between conductors, insulators and semiconductors.
  Even though the theory states that the conductivity is proportional to the free electron
concentration, itis found that divalent and trivalent metals are not good conductors.
However, monovalent metals Cu, Ag, Au, etc are good conductors.
 Some of the metals exhibit positive Hall coefficients, while the free electron theory
predicts negative hall coefficients for all the metals.
 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
andferromagnetism.

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 the electrical properties of
solidsbased on Fermi-Dirac statistics instead of Maxwell-Boltzmann statistics. He developed this
theory by
applying the principles of quantum mechanics.

Postulates (or) Salient features of Quantum Free Electron Theory

• Valence electrons move freely in a constant potential within the boundaries of metaland
is prevented from escaping the metal at the boundaries (high potential). Hence
theelectron 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.

The energy of electron is

Where n=1, 2, 3,…

Merits of quantum free electron theory

• 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
• 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.

Equation for electrical conductivity based on quantum free electron theory

When an electric field E is applied, the force on the elctrons is –eE. We know that force is also
rate of change of momentum dp/dt.
Fermi-Dirac distribution
The Fermi-Dirac distribution function, also called Fermi function. It provides the probability of
occupancy of energy levels by electrons /Fermions. Fermions are half-integer spin particles,
which obey the Pauli exclusion principle.
A metal piece contains very large number of electrons. Each electron possesses quantized
energy states and obeys Pauli’s exclusion principle. Hence, electrons satisfy Fermi- Dirac
statistics. The Fermi function F(E i ) provides the probability of electron occupied an energy level
at energy, E i in thermal equilibrium. The system is characterized by its temperature T and its
Fermi energyE F .
The probability F(E i ) of an electron occupying energy level E i is given by

Where F(Ei) is called Fermi function. Efis Fermi energy, Eiis energy of ithstate and k is
Boltzmann constant.
Temperature dependence of Fermi function

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,

then F(Ei)=1.
Which means 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 0Kis called Fermi Energy ‘E F ’and the energy level is known as Fermi
Level.
Case-3: At T>0K,
If, Ei=EF
Then,
F(Ei)=1/2.
Therefore Fermi level is the energylevel for which the probability of filled states is 50% at any
temperature.
If TFis theFermi temperature and VF is Fermi velocity corresponding to Fermi energy EF
Then,EF=kTF=>TF= EF/k
And

The electrons in the levels above EFare responsible for conduction. If the temperature is raised
further, the resistance of the metals increases due to decrease of mobility.
According to classical theory, all the free electrons below EFgain energy when
temperature is increased, which is deviates from the experimental observations. However,
according to quantum theory only few electrons below EFgain energy from external
source and thus theoretical values are closer to the experimental observations.
Density of states
Neglecting higher order terms, we get

The expression for nth energy level can be written as,

Differentiating Eq (4) by taking n and E as variable, we get

Substituting Eq (5) and (6) in Eq (3) we get,

V= a3, therefore, the density of states can be written as

 Band theory of Solids
Bloch theorem:
Bloch's theorem (1928) applies to wave functions of electrons inside a crystal and rests in the
fact that the Coulomb potential in a crystalline solid is periodic.

Statement: Bloch's theorem establishes that the wave function in a crystal, obtained

from Schrödinger's can be expressed as the product of a plane wave and a function
which has the same periodicity as the lattice
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

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

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

In the above equationUk(x) is called “modulating function”. Because free electron wave is
modulated by Uk(x) is periodic with the periodicity at the crystal lattice.
Case study
Consider a linear chain of atoms of length L in one-dimensional case with “N” number ofatoms
in the chain. Then,

Where ‘a’ is lattice distance

From equation (3) and (4),

This is referred to as Bloch condition.

Similarly, the complex conjugate of eq.(5) can be written as

From eq(5) and eq(6)

From this equation, it is clear that the electron is not localized around ones particular atom and
the probability of finding the electron is same throughout the crystal.
Therefore, in eq(5),

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.

Kronig-Penney model
Kronig-penny approximated the potentials of an electrons inside the crystal in terms of the
shapes of rectangular steps as shown, which is known as Kronig Penny model.
The periodic potential is taken in the form of rectangular one dimensional array of square
well potentials and it is the best suited to solve Schrodinger wave equation.
It is assumed that the potential energy is zero V(x) = 0inthe I-region and potential energy is V(x)
= 1, in the II-region.

i.e the Boundary conditions are

V(x) = 0, where x lies between o< x< a in region -I

V(x) = 1, where x lies between -b < x< 0 in region -II

This model explains many of the characteristic features of the behavior of electrons in a
periodic lattice.

The wave function related to this model can be obtained by solving Schrodinger equations
for the two regions,

Again,
The solution of these equations from Bloch theorem,

From figure, square well potentials, if 𝑉𝑉 o increases, the width of barrier ‘w’ decreases, if 𝑉𝑉 o
decreases the width of barrier w increases. But the (product) barrier strength
𝑉𝑉 o wremainsconstant.
To get this, differentiating above Schrodinger wave equations 3 & 4 w.r.to x, and by
applying boundary conditions of x (w.r.to their corresponding Ψ), to known the values of
constants
A, B of region -I, C,D-for reg-II,we get mathematical expression (by simplification).

--------(5)

P is called scattering power of the barrier and Voω is called barrier strength.

The left hand side of the equation (5) 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 the above figure, 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. Therefore, 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.

Brillouin Zone OR E-K diagram

The Brillouin zone are the boundaries that are marked by the values of wave vector k,in
which electrons can have allowed energy values. These represent the allowed values of k
of the electrons in 1D, 2D,&3D.
The energy of the electron in a constant potential box is,

It represents parabolic equation. A graph is drawn between the total energy (E) and the
wave vector k for various values of k.
It is the energy spectrum of an electron moving in presence of a periodic potential field
and is divided into allowed energy regions (allowed zones) or forbidden energy gaps
(forbidden zones).
Allowed energy values lie in the region k= -π/a to = +π/a. This zone is called the first
Brillouin zone. The break in the energy values is called forbidden energy band.The next
another allowed zone spread from k=-π/a to -2π/a and +π/a to +2π/a, which is called as
thesecond Brillouin zone. Similarly, the higher Brillouin zones are formed.

Classification of crystalline solids

Based on the width of forbidden band, solids are classified into conductors,
semiconductors, and insulators.

Conductors: The valence band and conduction bands are overlapped with each other
and the energy gap E g is zero. At room temperatures, free electrons already exist in huge
number at conduction band. 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 E g ≈ 1 eV. At low temperatures (0 K), free electrons are not available in
conduction band. These solids 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 E g = 1.1 ev, Germanium E g = 0.7ev.

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

Effective mass of electron

When an electron in a periodic potential of lattice is accelerated by an known electric

field or magnetic field, then the mass of the electron is called effective mass and is
represented by m∗.

To explain, let us consider an electron of charge ‘e’ and mass ‘m’ moving inside a
crystallattice of electric field E.
The acceleration a = eE / m is not a constant in the periodic lattice of the crystal.
It canbe considered that its variation is caused by the variation of electron’s mass when
itmoves in the crystal lattice.

Therefore, the acceleration of electron is given by

a = eE / m*
The electrical force on the electron is given by
F = m* a --------------(1)
By considering the free electron as a wave packet , the group velocity V g corresponding
tothe particle’s velocity can be written as
Comparing equations (1) and (3) we get,

This equation indicates that the effective mass is determined by

1) Variation of E with K: Variation of E withK corresponds to first Brillouin Zone.

Usingthis type of variation velocity can becalculated.
2) Variation of V with K: For K=0 velocity iszero and as k value increases V also
increasesreaching its maximum value at Koknown aspoint of inflexion. Beyond
Kovelocitydecreases and reaches to 0 at K=π/a.

3) 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
toπ/a. Beyond Kovelocity decreases and henceretarding force acts on electron and
itbehaves as positively charged particle referred to as hole.

4) Variation of fk:Degree of freedom of anelectron is defined as fk=m/m*.

fkismeasureof the extent to which the electron is free in astate K. If m* is large fkis
small, particlebehaves as heavy particle. If fk=1, electronbehaves as free electron.