Chapter 1

THEORY OF METAL
Elementary Quantum Mechanical Ideas

Quantum mechanics is a generalized form of mechanics applicable to very small objects like electron,
neutrons etc. in the atom. Classical mechanics are mainly applicable to large objects.

Various phenomena and process that take place within a material cannot be explained without having a
good knowledge on quantum mechanics. Although classical mechanics gives ideas about various
behavior of different objects, it fails to explain the material behavior for microscopic objects.

Q. Do sub-atomic particle obey Newton’s laws of motion?

A. The behavior of the sub-atomic particle cannot be described by Newton’s laws.

Wave Particle Duality: De Broglie’s Equation

When we deal about sub-atomic particles like electron, photon, neutron we experience that these sub-
atomic particle do not follow Newton’s laws of motion as well as they do not obey the Maxwell’s
Electromagnetic Theory as wave. This is because these sub-atomic particles behave as both wave as well
as particle.

It was observed that electromagnetic waves eg. X-rays, gamma rays, visible light etc. exhibit as similar to
properties of discrete particles of matter.
In 1924, Louis de Broglie presented his research thesis, in which he proposed electrons have properties
of both waves and particles, like light. The de Broglie equation is an equation used to describe the wave
properties of matter, specifically, the wave nature of the electron:

𝝀 = 𝒉/𝒑
𝒉
𝝀=
𝒎𝒗

where λ is wavelength, p is momentum of a particle, h is Planck's constant, m is the mass of a particle,

moving at a velocity v.

Also, 𝒑 = ℏ𝒌 and ℏ = 𝒉/𝟐𝝅

From above equations

𝒌 = 𝟐𝝅/𝝀 is a wave number.
The value of h = 6.624×10-34 Js

The electromagnetic radiation energy possessed by the photons in the form of packets is given by,
𝑬 = 𝒉𝒇 (known as Plank’s equation)
Also we know,
ℏ = 𝒉/𝟐𝝅

Thus, above equation can be written as,

 𝑬 = ℏ × 𝟐𝝅𝒇
𝑬 = ℏ𝝎 (ω is known as angular frequency)

There were two experiments conducted in early 20th century which were un explained by classical
mechanics and so warranted the need for quantum mechanical ideas.

Experiment 1

It was observed that beams of particle such as electrons were diffracted from a crystal in a manner
similar to the diffraction of x-rays, which are electromagnetic waves.

Experiment 2

By bombarding the material with photons the different energies, it was found that for each material a
characteristic energy is required to remove the electrons from the surface of material. The minimum
frequency of this electromagnetic radiation was found to be,

𝝓
𝒇=
𝒉
𝝓 𝒊𝒔 𝒄𝒂𝒍𝒍𝒆𝒅 𝒘𝒐𝒓𝒌 𝒇𝒖𝒏𝒄𝒕𝒊𝒐𝒏 𝒐𝒇 𝒎𝒂𝒕𝒆𝒓𝒊𝒂𝒍

These two experiments proved that the sub-atomic particle possessed the properties of both wave as
well as particle. Thus, wave-particle duality was developed.

Wave Function : Schrodinger’s Equation

Since, there is no clear distinction between wave and particle in quantum mechanics, there should be
some clear representation of what we call wave particle duality.

The displacement about its mean position is represented by wave-function 𝝍 as

−𝒋
[𝑬𝒕−𝒑𝒙]
𝝍 = 𝑨𝒆 ℏ ---- (i)

Where, A is maximum displacement from mean position or amplitude

ħ is h/2π

E is energy of a particle

p is momentum of particle

x is displacement from origin

Fig : ordinary wave represented by above equation

Differentiating equation (i) w.r.t x

−𝑗
𝜕𝜓 [𝐸𝑡−𝑝𝑥] 𝑗𝑝
= 𝐴𝑒 ℏ · ----- (ii)
𝜕𝑥 ℏ

Again differentiating equation (ii) w.r.t x

[𝐸𝑡−𝑝𝑥] 𝑗𝑝 2
−𝑗
𝜕𝜓
𝜕𝑥
= 𝐴𝑒 ℏ (ℏ)

𝜕𝜓 𝑝 2
= − ( ) 𝜓 ----- (iii)
𝜕𝑥 ℏ

For any system total energy E can be written as sum of kinetic energy and potential energy.
𝑝2
𝐸 = 2𝑚 + 𝑉

𝑝2
𝐸 − 𝑉 = 2𝑚

𝑝2 = 2𝑚(𝐸 − 𝑉) ----- (iv)

From equation (iii) and (iv)

𝜕𝜓 2𝑚(𝐸−𝑉)
𝜕𝑥
= −( ℏ2
) 𝜓

𝜕𝜓 2𝑚(𝐸−𝑉)
𝜕𝑥
+( ℏ2
) 𝜓 = 0 ------ (v)

When V is time independent then E is also time independent then equation (v) is known as time
independent S.W.E.
2𝑚[𝐸−𝑣]
In 3D 𝛻2 + ℏ
𝜓 =0
 𝜕2 𝜕2 𝜕2
Where, 𝛻 2 = 𝜕𝑥 2 + 𝜕𝑦2 + 𝜕𝑧2

When V is time dependent then E is also time dependent called SWE.

−𝑗
[𝐸𝑡−𝑝𝑥]
𝜓 = 𝐴𝑒 ℏ
Now, differentiating equation (i) wrt t we get,
−𝑗
𝜕𝜓 [𝐸𝑡−𝑝𝑥] 𝑗𝐸
𝜕𝑡
= −𝐴𝑒 ℏ · ℏ

𝜕𝜓 𝑗𝐸
=− 𝜓
𝜕𝑡 ℏ

𝜕𝜓
𝐸𝜓 = 𝑗ℏ 𝜕𝑡

Now, equation (v) can be written as,

𝜕𝜓 2𝑚𝐸 2𝑚𝑉
𝜕𝑥
+( ℏ2
) 𝜓−( ℏ2
) 𝜓=0

𝜕𝜓 2𝑚𝑉 2𝑚
−( ) 𝜓 = −( ) 𝐸𝜓
𝜕𝑥 ℏ2 ℏ2

ℏ2 𝜕𝜓 𝜕𝜓
2𝑚 𝜕𝑥
− 𝑉𝜓 = −𝑗ℏ 𝜕𝑡

In 3D
ℏ2 2 𝜕𝛹
𝛻 − 𝑉𝜓 = −𝑗ℏ
2𝑚 𝜕𝑡

This is time dependent SWE.

Wave Function (ψ)

The wave can easily be understood and represented in classical mechanics. But the wave function in
quantum mechanics does not have similar analogy. The wave function in quantum mechanics used to
describe the observable quantities in quantum mechanics.

In quantum mechanics energy, momentum and position of the particle are called observables and the
wave function ψ is used to describe these observables. These observables which characterize the
particle cannot be measured at the same instant i.e only one can be measured at once.

The wave function is extensively used to predict the probability that a particle would be found in a
specified volume of space. Wave function is a complex three dimensional quantity and is dependent
upon the time. If ψ(x,y,z,t) represents the wave function then | ψ|2 is called probability amplitude.

The probability of finding the particle in given incremental volume is equal to the probability amplitude
(also called probability density function) and incremental volume i.e
 | ψ(x,y,z)|2dx dy dz

The probability of locating the particle between x and x+dx in single dimensional case, then the
probability will be equal to | ψ(x)|2dx.

Mathematically, for a particle located somewhere in the universe, we can write

+∞
∫ 𝛙 (𝐱, 𝐭)𝐝𝐱 = 𝟏
−∞

 Schrodinger’s equation does not tell us about the position of the particle rather it only gives us
the probability of finding the particle in the vicinity of a point.
 A free particle is that which is not confined to any location. If potential energy V=0 in
Schrodinger’s equation for a particle in one-dimensional case is given by,
𝜳𝜳∗ = |𝑨|𝟐

Electron in infinite potential well

Fig : electron in infinite potential well

Let us consider an electron is present in the region 0<x<a where, a represents the width of the region in
which electron is confined. Assume the potential energy of the particle is zero inside the confined region
and infinite outside it. The electron thus confined cannot leave the region because to leave, it requires
infinite potential energy.

Boundary condition for potential energy is given by

0 0<𝑥<𝑎
𝑉={
∞ 0 ≥ 𝑥, 𝑎 ≤ 𝑥
Ψ is continuous function, so Ψ(0) = Ψ(a) = 0
Schrodinger’s equation inside the box is given by,

𝜕𝜓 2𝑚𝐸
𝜕𝑥
+( ℏ2
) 𝜓=0

𝜕𝜓
𝜕𝑥
+ 𝑘 2 𝜓 = 0 ------- (i)

Where,
2𝑚𝐸
𝑘2 = ( ℏ2
)

General solution for equation (i)

𝜓(𝑥) = 𝐴𝑠𝑖𝑛𝑘𝑥 + 𝐵𝑐𝑜𝑠𝑘𝑥 …… (ii)

Where, A and B are some constants which we can find from boundary conditions.

We know from boundary;

𝜓(𝑥) = 0 for 𝑥 = 0

here,

0= 𝐴·0+𝐵·1
𝐵=0
Again,

𝜓(𝑥) = 0 for 𝑥 = 𝐿

0 = 𝐴𝑆𝑖𝑛𝑘𝐿
Since, 𝐴 ≠ 0 then sin 𝑘𝐿 = 0 = sin 𝑛𝜋

When 𝑛 = 1,2,3 … . . ∞

𝑘𝐿 = 𝑛𝜋
𝑛𝜋
𝑘= 𝐿

Now, from equation (ii)

𝑛𝜋
𝜓(𝑥) = 𝐴 sin 𝑥
𝐿

To find the value of A above equation can be normalized as;

𝐿
∫0 |𝜓|2 𝑑𝑥 = 1
𝐿 𝑛𝜋
∫0 𝐴2 𝑠𝑖𝑛2 𝐿
𝑥 𝑑𝑥 =1
𝐿 𝑛𝜋
∫0 𝐴2 (1 − 2cos 𝐿
𝑥)𝑑𝑥 =1
𝐴2 𝐿
2
𝑥|0 =1
1
2 2
𝐴= ( )
𝐿

The normalized wave function of the electron in the box is;

1
2 2 𝑛𝜋
𝜓𝑛 = ( ) sin 𝑥
𝐿 𝐿

This is called Eigen’s function and value is used to measure the total energy of the particle inside the
box.
2𝑚𝐸 8𝜋2 𝑚𝐸
𝑘2 = ( ℏ2
) = ℎ2

𝑘 2ℎ2
𝐸 = 8𝜋2 𝑚

Fig: Energy level and wave function in the well

Finite Potential Barrier

Fig : finite potential barrier

Consider a particle travelling in positive x-direction and encounters a barrier whose potential energy is
V0. Here, energy of the particle is less than the barrier potential energy also known as barrier height.

When applying Schrodinger’s equation for the electron, here, we have to take into account the fact that
there are two distinct region where the behavior of electron will be different.

In region 1st electron is free. So, it’s potential energy is set equal to zero. So the Schrodinger’s equation
for region I will be,

𝜕𝜓1 2𝑚𝐸
𝜕𝑥
+( ℏ2
) 𝜓1 = 0 -------- (i) for x<0

For region II, x>0

We can write Schrodinger’s equation as

𝜕𝜓2 2𝑚(𝐸−𝑉0 )
+( ) 𝜓2 = 0 -----------(ii)
𝜕𝑥 ℏ2

Above equations can be written as,

𝜕𝜓1
+ 𝛽 2 𝜓1 = 0-------------- (iii)
𝜕𝑥

𝜕𝜓2
𝜕𝑥
+ 𝛼 2 𝜓2 = 0 ------------ (iv)

Where,
2𝑚𝐸 2𝑚(𝐸−𝑉0 )
𝛽2 = 𝛼2 =
ℏ2 ℏ2

The solution of equation (iii) and (iv) can be written as,

𝜓1 = 𝐴𝑒 𝑗𝛽𝑥 + 𝐵𝑒 −𝑗𝛽𝑥 --------(v)

𝜓2 = 𝐶𝑒 𝑗𝛼𝑥 + 𝐷𝑒 −𝑗𝛼𝑥 --------- (vi)

Where,

𝐴𝑒 𝑗𝛽𝑥 = wave travelling in +ve x-direction

𝐵𝑒 −𝑗𝛽𝑥 = wave reflected from potential barrier

𝐶𝑒 −𝑗𝛼𝑥 = exponential increasing wave that penetrates the barrier in +ve x-direction

𝐷𝑒 −𝑗𝛼𝑥 = exponential decreasing wave that penetrates the barrier

According to physics, interpretation 𝜓 must be finite only and only if exponential increasing wave does
not exists after the penetration of the barrier.

i.e. C=0

Now, the constant A, B and D in above equation (v) and (vi) can be found by using boundary condition.

At x=0, both the wave functions are continuous. So they must be equal to each other,

𝜓1 (0) = 𝜓2 (0)

𝐴𝑒 𝑗𝛽0 + 𝐵𝑒 −𝑗𝛽0 = 𝐷𝑒 −𝑗𝛼0

𝐴 + 𝐵 = 𝐷 -------- (vii)

The second boundary condition is the slope of both the wave function at x=0 are continuous
𝜕𝜓1 𝜕𝜓2
| = |
𝜕𝑥 𝑥=𝑜 𝜕𝑥 𝑥=𝑜
𝑗𝐴𝛽𝑒 𝑗𝛽𝑥 − 𝑗𝐵𝛽𝑒 −𝑗𝛽𝑥 = −𝑗𝐷𝛼𝑒 −𝑗𝛼𝑥

𝑗𝐴𝛽𝑒 𝑗𝛽0 − 𝑗𝐵𝛽𝑒 −𝑗𝛽0 = −𝑗𝐷𝛼𝑒 −𝑗𝛼0

𝑗𝐴𝛽 − 𝑗𝐵𝛽 = −𝑗𝐷𝛼 -------- (viii)

From (vii) and (viii) we get,

𝐷 𝛼
𝐴 = 2 [1 − 𝛽]

𝐷 𝛼
𝐵 = 2 [1 + 𝛽]

According to the classical mechanics no particle can enter in region IInd but quantum mechanics proves
that wave function has a finite value in region IInd wave function decreases exponentially in region IInd .

Fig : particle wave function in different region

Tunneling Effect

When beam of particle of energy ‘e’ is incident on the left of the potential barrier of height (V0(V0>E)).
According to the classical mechanics the probability of any particle crossing the barrier is impossible.
However, according to the quantum mechanics there is probability of the crossing the barrier. This
behavior is called tunneling effect.
Fig : electron wave length in different region

In region 1, the Schrodinger’s equation is

𝜕𝜓1
𝜕𝑥
+ 𝛽 2 𝜓1 = 0 -------- (i)

And the solution is,

𝜓1 = 𝐴𝑒 𝑗𝛽𝑥 + 𝐵𝑒 −𝑗𝛽𝑥 ------ (ii)

In region 2, the wave function is,

𝜕𝜓2
𝜕𝑥
+ 𝛼 2 𝜓2 = 0 --------- (iii)

𝜓2 = 𝐷𝑒 −𝑗𝛼𝑥 ----------- (iv)

Similarly, in region 3, the Schrodinger’s equation is,

𝜕𝜓3
+ 𝛽 2 𝜓3 = 0 ----------- (v)
𝜕𝑥

And the solution is,

𝜓3 = 𝐹𝑒 𝑗𝛽𝑥 + 𝐺𝑒 −𝑗𝛽𝑥 ------------ (vi)

Where,
2𝑚𝐸
𝛽2 = ℏ2

2𝑚(𝐸−𝑉0 )
𝛼2 = ℏ2

𝐴𝑒 𝑗𝛽𝑥 = wave travelling in +ve x-direction

𝐵𝑒 −𝑗𝛽𝑥 = wave reflected from potential barrier

𝐷𝑒 𝑗𝛼𝑥 = exponential decrease wave that penetrates the barrier

𝐹𝑒 𝑗𝛽𝑥 = wave travelling in +ve x-direction onwards

𝐺𝑒 −𝑗𝛽𝑥 = wave reflected from region 3 which practically and theoretically does not exists = 0

The relative probability at the electron will turned from region 1 to region 3 through 2 is defined as
transmission coefficient (T) which depends very strongly both on the relative potential barrier height
(V0-E) and the width of the potential barrier. The final expression for the transmission coefficient is
expressed as,
|𝜓3 (𝑥)|2 𝐹2
𝑇= |𝜓1 (𝑖)|2
= 𝐴2

1
𝑇 = 1+𝐷𝑠𝑖𝑛ℎ2 (𝛼𝐿)

𝑉2
𝐷 = 4𝐸(𝑉0 −𝐸)
0

On solving we get,
16𝐸(𝑉0 −𝐸) −2𝛼𝐿
𝑇= 𝑉02
𝑒

And the reflection coefficient R is given by,

𝐵2
𝑅= =1−𝑇
𝐴2

Pauli Exclusion Principle

It states that “no two electrons in any one atom can have all four identical quantum number”.

Where,

n = principle quantum number

l = orbital angular momentum quantum number

ml = magnetic quantum number

ms = spin magnetic quantum number

and the wave function is given by, 𝜓𝑛,l,𝑚𝑙,𝑚𝑠 ,

According to the principle there must be at least one of the quantum number different than other in an
electrons of an atom. If four quantum numbers of two electrons are identical, the one of the two
electrons will be excluded from the electronic configuration of an atom. Therefore, this principle is
called exclusion principle.
Free Electron Theory Of Metal

Drude in 1990 constructed theory of metal on the basis of kinetic theory of gases.

In gas a single type of particle is present but in metal at least two types of particles are present. i.e.
electron and protons.

According to this theory the outermost electrons of metal known as valance electrons of atoms are
loosely attached to the parent atom and these electron are free to move throughout the whole metal
forming gas.

Momentum (𝑝) = 𝑚𝑣
1 𝑝2
Kinetic energy of electrons (𝐾𝐸)= 2 𝑚𝑣 2 = 2𝑚

We have,

𝑝 = ℏ𝑘
(ℏ𝑘)2
𝐾𝐸 = 2𝑚

𝐾𝐸 = 𝑐𝑘 2
ℏ2
Where, 𝑐 = 2𝑚

Fermi Energy

Fermi energy is defined as the highest filled energy level at a temperature of absolute zero. i.e.00K. All
the energy levels up to the fermi level are filled at 00K and empty above it. The distribution of electron
among various energy level in accordance with Pauli’s exclusion principle. If N is the total numbers of
electrons to be accommodated on the line then for even n, we have 𝑁 = 2𝑛𝑓 . Thus, for 𝑛 = 𝑛𝑓 the
expression can be written as,
 ℏ2 𝜋𝑛𝐹 2
𝐸𝐹 = ( ) ------ (1)
2𝑚 2

Thus, the fermi energy depends upon the length of the box and the number of electrons in the box.
ℏ2 𝜋𝑁 2 ℏ2
𝐸𝐹 = 2𝑚 ( 2𝐿
) = 2𝑚 𝐾𝐹2

Where, Kf = Fermi-wave vector

nf = principle quantum number of the fermi level

The number of occupied electrons is sphere is given by;

𝑉𝑜𝑙. 𝑜𝑓 𝑠𝑝ℎ𝑒𝑟𝑒 𝑜𝑓 𝑟𝑎𝑑𝑖𝑢𝑠 𝐾𝐹
𝑁 = 2 × 𝑉𝑜𝑙. 𝑜𝑓 𝑒𝑙𝑒𝑚𝑒𝑛𝑡 𝑜𝑓 𝐾−𝑠𝑝𝑎𝑐𝑒

4⁄ 𝜋𝐾3
3 𝐹
𝑁 =2× 𝐾𝑥3

𝐿3 𝐾3 2𝜋
𝑁= 3𝜋2
(𝐾𝑥 = 𝐿
)

𝑉𝐾3
𝑁= 3𝜋2

𝑁 𝐾𝑓3
And 𝑛 = =
𝑉 3𝜋3

Operators

Operators are used to predict the parameters like energy, momentum and position of an electron.

We have, SWE
−𝑗
[𝐸𝑡−𝑝𝑥]
𝜓 = 𝐴𝑒 ℏ
Differentiating w.r.t t
−𝑗
𝜕𝜓 [𝐸𝑡−𝑝𝑥] 𝑗𝐸
𝜕𝑡
= −𝐴𝑒 ℏ · ℏ

𝜕𝜓 𝑗𝐸
𝜕𝑡
=− ℏ
𝜓
𝜕𝜓
𝐸𝜓 = 𝑗ℏ 𝜕𝑡

𝜕
This 𝐸 → 𝑗ℏ 𝜕𝑡 is called energy operator.

Similarly, differentiating w.r.t x.

 −𝑗
𝜕𝜓 [𝐸𝑡−𝑝𝑥] 𝑗𝑝
𝜕𝑥
= 𝐴𝑒 ℏ · ℏ

Degenerate State

Different combination of principle quantum number representing the same energy is called degenerate
𝑛2 ℏ2
state. The energy of electron in potential well is 𝐸 = 8𝑚𝐿2 . Here, principle quantum number ‘n’ is taken
for single dimension and for three dimension, 𝑛2 = 𝑛𝑥2 + 𝑛𝑦2 + 𝑛𝑧2 .
ℏ2
Then, the energy can be expressed as, 𝐸𝑛 = 8𝑚𝐿2 𝑛𝑥2 + 𝑛𝑦2 + 𝑛𝑧2.

For same value of equation ‘n’ along x-axis can represent different energy because it also depends on ‘n’
along y and z-axis.

For example (1,2,1), (2,1,1) and (1,1,2) represent same electron energy. These all three electronic state
are degenerate states.

Heisenberg’s Uncertainty Principle

It is impossible to determine both position and momentum of an electron simultaneously with perfect
accuracy. If an experiment is designate to measure one of them exactly, the other will become uncertain
and vice-versa.

Let ∆𝑥 be the uncertainty to introduce in measuring the position and ∆𝑝 be the uncertainty to introduce
in measuring momentum. If we try to measure both at once then according to uncertainty principle.
ℏ
∆𝑥∆𝑝 ≥ 2
ℎ
Where, ℏ = 2𝜋 , ℎ Plank’s constant.

Definition Of Number Of States, Density Of States

The quantized energy state of electron is ;

𝑛2 ℏ2
𝐸 = 8𝑚𝐿2

ℏ2
𝐸𝑛 = 8𝑚𝐿2 𝑛𝑥2 + 𝑛𝑦2 + 𝑛𝑧2

Each set of quantum number exists a specific energy level called energy state. For nx=ny=nz=1, there is
one energy state. So unit cube has one energy state. Hence the number of energy state in any energy
volume is proportional to that value.
The principle quantum number takes only positive value so it takes only radius ‘n’. The number of
energy state within the sphere of radius ‘n’ is,

1 4𝜋𝑛3
𝑁=
8 3
Also,
𝑛2 ℏ2
𝐸 = 8𝑚𝐿2

8𝑚𝐿2 𝐸 = 𝑛2 ℏ2

8𝑚𝐿2 𝐸
𝑛=√ ℏ2

Now,
3⁄2
1 4𝜋 8mL2 𝐸
𝑁= · [ 2 ]
8 3 ℏ
𝜋
𝑁 = 6 · 𝐾 3⁄2 𝐸3⁄2

Where,
8𝑚𝐿2
𝑘= ℏ2

The number of state represent the number of energy level in quantum space. The density of states is
number of energy state per unit energy in an energy interval of dE.
3 1
𝑑𝑁 3𝜋
𝑑𝐸
= 2 6 𝐾 2𝐸2
3 1
𝑑𝑁 𝜋
= 𝐾 2𝐸2
𝑑𝐸 4
𝑑𝑁
Here, 𝑑𝐸 = 𝑍(𝐸) = 𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑡𝑎𝑡𝑒

When electron is placed in potential box with side ‘l’ then the volume of box is,

𝑉 = 𝑙3
We have,
3 1
𝑑𝑁 𝜋
𝑍(𝐸) = = 𝐾 2𝐸2
𝑑𝐸 4

3⁄2 1
𝑑𝑁 𝜋 8mL2
𝑍(𝐸) = 𝑑𝐸
= 4[ ℏ2 ] 𝐸2

𝑑𝑁 𝜋 2𝑚 3⁄2 1
𝑍(𝐸) = 𝑑𝐸
= 4 4 [ ℏ2 ] 𝐸2𝑉
 𝑑𝑁 2𝑚 3⁄2 1
𝑍(𝐸) = 𝑑𝐸
= 2𝜋𝑉 [ ℏ2 ] 𝐸2
1
𝑍(𝐸) = 𝐶𝐸 2
2𝑚 3⁄2
Where, 𝐶 = 2𝜋𝑉 [ ℏ2 ]

Fig: Density of state vs energy function

In the figure, the curve representing Z(E) is hyperbola where all energy levels less than E(n) are taken
into account. The shaded area represents the number of energy state in an elementary energy interval
d(E).

dN=Z(E)=dE

Contact Potential

Each metal has different work function which makes their fermi level different. When metal with
different fermi level are in contact then electrons from metal with higher fermi level moves towards
lower fermi level. This transfer of electron from higher fermi level to lower fermi level makes it
positively charge and metals with low fermi level becomes negatively charge. Finally, a potential
difference is developed at junction called contact potential. This process continues till the contact
potential is large enough to prevent the further transfer of electron.

This is called system at equilibrium. The contact potential due to difference in work function can be
calculated as;

𝑒∇𝑣 = ∅2 − ∅1
∅2 −∅1
∇𝑣 = 𝑒

Thermal Emission And Work Function

The process of ejection of electrons from the surface of the metal at rather high temperature is called
thermal emission. There is a threshold(minimum) value of energy which electron must possess if it is to
leave the metal surface. The threshold value of energy is called work function of the metal. Work
function is denoted by Greek alphabet φ.

Fig: Fermi-level and work function in metal

In 1901 Richardson published the results of this experiment, the current from a heated wire seemed to
depend exponentially on the temperature of the wire. A mathematical form similar to Arrhenius
equation. Later he proposed that the emission law should have the mathematical form,

𝐼 = 𝐴𝐺 𝑇 2 𝑒 −∅⁄𝐾𝑇
I is emission current

T is temperature of the metal

φ is work function of the metal

K is Boltzman’s constant

There was no consensus among interested theoreticians as to what is the exact expression for AG but
there is agreement that AG must be written in the form,

𝐴𝐺 = λ𝑅 𝐴0
Where, λR is a material specific correction factor that is typically of order 0.5 and A0 is a universal
constant given by,
4𝜋𝑚𝑘 2 𝑒
𝐴0 = ℎ3

Where, m and e are the mass and charge of an electron and h is plank’s constant.

Fermi-Dirac Distribution

Let us consider state of two particle with wave function ψ1 and ψ2 and their corresponding energy E1
and E2. This two particles goes on interaction or collision and they change their state.
Now, above particles have wave function ψ3 and ψ4 and their corresponding energy value E3 and E4
respectively after collision.

Now, after collision,

𝑓(𝐸1 )𝑓(𝐸2 )[1 − 𝑓(𝐸3 )][1 − 𝑓(𝐸4 )] = 𝑓(𝐸3 )𝑓(𝐸4 )[1 − 𝑓(𝐸1 )][1 − 𝑓(𝐸2 )]------ (1)

𝐹𝑜𝑟𝑤𝑎𝑟𝑑 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 = 𝐵𝑎𝑐𝑘𝑤𝑎𝑟𝑑 𝑝𝑟𝑜𝑐𝑒𝑠𝑠

∈1 +∈2 =∈3 +∈4
Now, the fermi-Dirac distribution function is given by,
1
𝐹(𝐸) =
1+𝑒 (𝐸−𝐸𝐹 )⁄𝑘𝑇

Where,

F(E) = Occupation index or probability of occupation

E = Energy of the electron

EF = Fermi energy level

T = Absolute temperature

k = Boltzmann’s constant

Case I : When T=0 and EF>>E

1
𝐹(𝐸) = 1+𝑒 −∞
𝐹(𝐸) = 1
Case II : When T=0 and EF<<E
1
𝐹(𝐸) = 1+𝑒 ∞

𝐹(𝐸) = 0
Case III : When 𝑇 ≠ 0 , Ef=E
1 1
𝐹(𝐸) = 1+𝑒 0 = 2

Case IV : When 𝑇 ≠ 0 , Ef<E

1 1
𝐹(𝐸) = 1+𝑒 𝐸⁄𝑘𝑇 = 𝑒 𝐸⁄𝑘𝑇

By using Fermi function or occupation index we can calculate the number of energy occupied by the
electron.

Fig : Fermi Dirac distribution