Bonds to Bands

UNIT-1

ATOMICBONDS
AND MOLECULAR
TO BANDS STRUCTURE

Introduction to quantum chemistry – Motion of a quantum mechanical particle in

one dimension (time- independent) – Schrödinger wave equation for hydrogen
atom (No derivation) – Physical meaning of wave function - Angular and radial
wave functions and probability densities – Quantum numbers – Principal,
azimuthal, spin and magnetic quantum numbers – Wave functions and
orbital shapes - s,p,d,f - LCAO-MO of H2 – Band theory ofsolids: Conductors,
semi-conductors and superconductors – Role of As and Ga doping on band
structures.

1.1 INTRODUCTION

In this chapter, we shall give an overview of the properties of solids and how
quantum mechanics helps us to understand these properties. In the solid state, a
material at a given temperature and pressure has a well definite shape. The forces of
interaction between the atoms in the solid must be strong and the bonds between them
are stable under existing conditions. In subsections, we used quantum mechanics to
understand how these bonds are formed. We have considered the crystalline solids, in
which the bonds allow the formation of regular arrays of atoms within the solid. In
other subsections, we give an introductory treatment of energy bands and the band
theory of solids to explain the electrical conductivity and why some solids are
conductors, whereas others are semiconductors or insulators.

Most important among these is the idea of a bond, and the use of frontier-
orbital arguments. Interpretative constructs, such as the density of states, the
decomposition of these densities and crystal orbital overlap population, allow a

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Bonds to Bands
recovery of bonds, a finding of the frontier orbitals that control structure and reactivity
in extended systems as well as discrete molecules.

1.2 ELECTROMAGNETIC WAVE

Electromagnetic wave or radiation is a wave that consists of oscillating electric

and magnetic fields which is characterized by wavelength λ and frequency ν (number
of oscillations per second). The wavelength and frequency of the wave is related to
velocity c (3 x 108 ms-1) of the wave by 𝑐 = 𝜆𝜈

1.3 BLACK BODY RADIATION

Fig 1.1 Black body radiation

An ideal black body is an object that absorbs all the radiations falling on it. A
hollow enclosure or chamber having a small hole is anappropriate black body because
it absorbs all the radiation entering it due repeated reflections inside the enclosure. The
radiation emitted from such a black body is called black body radiation. A perfect
absorber is also a perfect emitter of radiation. The intensity of the total radiation
emitted per unit surface area from a black body depends on temperature T and is
independent of the nature of the solid.
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Bonds to Bands
1.3.1 Laws of Radiation

The radiation emitted by a heated body is explained by the laws of radiation.

1.3.1.1 Wien’s law

The wavelength λm corresponding to the maximum energy density ρ(ν)dν is

inversely proportional to the temperature T.

1
𝜆𝑚 ∝
𝑇

𝑏
𝜆𝑚 =
𝑇

𝜆𝑚 𝑇 = 𝑏

where b is called Wien’s constant and value of b is 2897 microkelvin.

1.3.1.2 Rayleigh-Jean’s law

Rayleigh derived an equation for the distribution of energy densitycalled the

Rayleigh-Jean’s law

8𝜋𝜈 2
𝜌(𝜈)𝑑𝜈 = 𝐾 𝑇𝑑𝜈
𝑐3 𝐵

whereρ(ν)dν is the energy density and KB is the Boltzmann constant

(1.38  10-23 JK-1).

1.3.1.3 Planck’s law of radiation

Max Planck derived an expression for energy density of a black body radiation
called as Planck’s radiation law and is given by

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Bonds to Bands
8𝜋ℎ𝜈 3 1
𝜌(𝜈)𝑑𝜈 = 3 (ℎ𝜈
𝑑𝜈
𝑐 (𝑒 ⁄𝐾𝐵 𝑇 ) − 1)

Planck introduced a constant h known as Planck’s constant (value of

h = 6.626  10-34Js). He proposed the Planck’s quantum theory based on energy
quantization to explain the black body radiation.

Fig 1.2 Planck’s law of black body radiation

The black body emits radiation in a wide spectrum of wavelengths. The

distribution of energy of emitted radiation over different frequencies is called as energy
density and is given by ρ(ν)dν. At any temperature T, the energy density ρ(ν)dν
increases with increase in ν, reaches a maximum and then drops to zero. With increase
in T, the maximum of curve shifts to higher frequency (i.e) shorter wavelength side.

Planck’s quantum theory of radiation

According to this theory

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Bonds to Bands
1. Energy is absorbed or emitted in the form of discrete sets of small bundles of
energy known as quanta.
2. Each quantum is associated with certain amount of energy E = hν, where h is
Planck constant and ν is the frequency of radiation.
3. A body can emit or absorb energy only in integral multiples of quantum (i.e)
1hν, 2hν, 3hν………nhν.

1.4 PHOTOELECTRIC EFFECT

In 1905, based on the Planck’s idea of energy quantization, Albert Einstein

discovered law of the photoelectric effect.According to photoelectric effect, when a
light photon of a certain frequency ν strikes the surface of metal, electrons are emitted
from the metal. The photon transfers its energy hν to the electrons and this is used to
1
overcome the binding energy (ω) and to increase kinetic energy(2 𝑚𝓋 2 ) of the emitted
electrons.

1
ℎ𝜈 = 𝜔 + 𝑚𝓋 2
2

since 𝜔 = ℎ𝜈0 , where ν0 is the threshold frequency

1
ℎ𝜈 = ℎ𝜈0 + 𝑚𝓋 2
2

1
𝑚𝓋 2 = ℎ𝜈 − ℎ𝜈0
2

1
𝑚𝓋 2 = ℎ(𝜈 − 𝜈0 )
2

This equation is called the Einstein photoelectric equation

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Bonds to Bands

Fig 1.3 Photoelectric effect

Observations

1. Light with minimum frequency called the threshold frequency ν0 is necessary

to cause emission of electron by photoelectric effect. (If ν <ν0 there is no
photoelectric effect)
2. Kinetic energy of emitted electrons is directly proportional to frequency and
independent of intensity of incident radiation.

1.5 WAVE – PARTICLE DUALITY OF ELECTRON – de BROGLIE’S

HYPOTHESIS

Louis de Broglie in 1924 proposed that the quantization of energy of an atom

can be explained only when electrons exhibit wave-particle dual behaviour. This
hypothesis was verified through electron diffraction experiment by Davisson and
Germer. The electrons produce diffraction patterns similar to light waves when passed
through a nickel crystal which confirms the wave nature of electrons. de Broglie
hypothesis can be derived by using Einstein’s energy mass relationship

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Bonds to Bands
𝐸 = 𝑚𝑐 2 (1)

where c is velocity of photon and m is mass of photon.

According to Planck, the energy of photon is quantized which inherently possess the
duality nature of particle, since energy of photon E is a particle property and frequency
ν is a wave property.

𝐸 = ℎ𝜈 (2)

Thus from equations (1) and (2)

𝑚𝑐 2
ℎ𝜈 = 𝑚𝑐 2 ⇒ 𝜈 =
ℎ

In wave theory of light, the frequency ν and wavelength λ is related to each other by
the equation 𝜈𝜆 = 𝑐

Therefore,
𝑐 𝑐ℎ ℎ ℎ
𝜆= = = =
𝜈 𝑚𝑐 2 𝑚𝑐 𝑝

wherep is the momentum of the photon p = mc

de Broglie proposed that the wavelength or frequency of electron similar to the photon
is related to the momentumof the electron

ℎ ℎ
𝜆= 𝑜𝑟
𝑚𝑐 𝑝

where λ = wavelength of electron, m = mass of electron, p = momentum of electron, h

= Planck’s constant.

de Broglie hypothesis of wave-particle duality is applicable to all subatomic

particles such as neutrons, protons etc.

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1.6 HEISENBERG’S UNCERTAINTY PRINCIPLE

Heisenberg stated that “it is not possible, even in principle to measure both
position and momentum of an electron simultaneously”. This is known as Heisenberg
uncertainty principle. Mathematically it is expressed as

ℎ
∆𝑥 . ∆𝑝 ≥
4𝜋

Where∆x is the uncertainty in position of the electron, ∆p is the uncertainty in

momentum of the electron and h is the Planck’s constant. If the position of an electron
is determined with high accuracy then its momentum becomes uncertain. Similarly, if
the momentum of the electron is measured precisely then its position will be uncertain.
This principle holds good only for microscopic particles however, it does not apply to
larger bodies (i.e) both momentum and position can be determined accurately at the
same time.

1.7 THEORY OF WAVE MOTION

The de Broglie, Heisenberg uncertainty principle and electron diffraction

experiments established the dual nature of electrons as particle as well as wave. A
particle is localized and it cannot be present in more than one place at same time
whereas wave cannot be localized at a point and varies from a point to point in space.
In order to insight the behaviour of electrons it is necessary to understand the
characteristics of wave motion.

1.7.1 Classical Waves and Wave Equation

Consider the wave motion in vibration of a string, the vertical displacement of

string from its mean position and is called the amplitude of wave or vibration. This
amplitude is a function of position (x) and time (t) and denoted as Ψ(x,t).

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Bonds to Bands

Fig 1.4 Classical wave

Here the wave makes same amplitude at regular intervals of ∆x which is λ the
wavelength of the wave.The velocity of wave c is given by λ/t, the frequency ν (number
of waves per unit time) will be c = λ/t ⇒ 1/t = c/λ⇒ ν = c/λ and the wave number
(number of waves per unit distance) will be ῡ = 1/λ. The periodic nature of Ψ(x,t)
propose the sine or cosine function of x and t where x is position coordinate and t is
time coordinate. The expression for wave function is obtained by solving the equation
of the wave motion which is not in the scope of this book

𝜕2𝛹 1 𝜕2𝛹
= (1)
𝜕𝑥 2 𝑐 2 𝜕𝑡 2

where Ψ=Ψ(x,t). By applying separation of variables method, function Ψ(x,t) is

separated into a product of two functions

𝛹(𝑥, 𝑡) = 𝛹(𝑥). 𝛷(𝑡) (2)

where Ψ(x) is a function of x only and Φ(t) is a function of t only. Substituting equation
(2) in (1) and diving by Ψ(x). Φ(t) on both sides gives

𝑐2 𝜕2𝛹 1 𝜕2𝛷
. = . (3)
𝛹 𝜕𝑥 2 𝛷 𝜕𝑡 2
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Bonds to Bands
The left hand side of equation (3) depends only on x and right hand side depends only
on t however both sides are equal and are equated to a constant -k2

𝑐2 𝜕2𝛹 1 𝜕2𝛷
. = . = −𝑘 2 (4)
𝛹 𝜕𝑥 2 𝛷 𝜕𝑡 2

Thus two equations are obtained from equation (4)

𝜕2𝛹 𝑘2
=− 2 𝛹 (5)
𝜕𝑥 2 𝑐

𝜕2𝛷
= −𝑘 2 𝛷 (6)
𝜕𝑡 2

Here equation (5) is the time-independent wave equation called as amplitude equation.
The general solutions for equations (5) and (6) are

𝑘𝑥 𝑘𝑥
𝛹(𝑥) = 𝐴 𝑠𝑖𝑛 ( ) + 𝐵𝑐𝑜𝑠 ( ) (7)
𝑐 𝑐

𝛷(𝑡) = 𝐶 sin(𝑘𝑡) + 𝐷 cos(𝑘𝑡) (8)

where A,B,C and D are arbitrary constants.

The other solutions of equation (5) are

2𝜋𝑖𝑥
𝛹(𝑥) = 𝐴 exp (± ) (9)
𝜆

These exponential functions are expressed in trigonometric functions as

exp(±𝑖𝑘𝑥) = 𝑐𝑜𝑠𝑘𝑥 ± 𝑖 𝑠𝑖𝑛𝑘𝑥 (10)

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Bonds to Bands
1.7.2 Stationary Waves

Waves expressed by the equation (5) are called running waves in which Ψ is a
function of time. However, electron waves in atoms and molecules are stationary
waves in which Ψ does not change with time. A classical example of such wave is the
wave in a vibrating string clamped at two ends.

Thus equation (5) may be expressed as

𝜕2𝛹 4𝜋 2
=− 2 𝛹 (11)
𝜕𝑥 2 𝜆

From classical waves we know that

𝑘 2𝜋
=
𝑐 𝜆𝑐

2𝜋
∴k=
𝜆

Equation (7) becomes

2𝜋𝑥 2𝜋𝑥
𝛹(𝑥) = 𝐴 𝑠𝑖𝑛 ( ) + 𝐵𝑐𝑜𝑠 ( ) (12)
𝜆 𝜆

Hence the wave does not vibrate at the ends x = 0 and x = L and this is called as
boundary conditions.

The first boundary condition x = 0, Ψ becomes 0 from equation (12) and B becomes
zero

2𝜋 2𝜋
0 = 𝐴 𝑠𝑖𝑛 ( .0) + 𝐵𝑐𝑜𝑠 ( .0) = 𝐵 (13)
𝜆 𝜆

The second boundary condition on equation (13) is x = L and B = 0, ∴Ψ becomes 0

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Bonds to Bands

2𝜋
0 = 𝐴 𝑠𝑖𝑛 ( . 𝐿) (14)
𝜆

Fig 1.5 Stationary wave - Vibration in clamped string

Equation (14) is satisfied when

1. A = 0, but Ψ becomes zero everywhere and for all values of x which is not
acceptable.

2𝜋 2𝐿
2. 𝜆
. 𝐿 = 𝑛𝜋, where n = 0, ±1, ±2, ±3 …or 𝜆 = 𝑛
and is acceptable.

𝑛𝜋𝑥
The solution of the wave equation is 𝛹 = 𝐴 sin where A is maximum amplitude
𝐿
of the wave. The equation becomes zero at boundary conditions and integral number
of half wavelength between the clamped ends of the string. The points where Ψ
becomes zero is called node.

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Bonds to Bands
For example when n = 0, Ψ = 0 everywhere, when n = 1, Ψ = 0 only at x = 0 and x =
L, and there is no node, when n = 2, Ψ becomes zero at x = L/2 which is a node, for n
= 3, Ψ becomes zero at x = L/3 and 2L/3 thus two nodes are present and so on.

1.7.3 Schrodinger Equation for Particle Waves

Erwin Schrodinger proposed that if electrons have both particle and wave
behaviour the equation of wave motion can be applied to them. He used the time-
independent wave equation to explain the particle wave. For an electron of wavelength
λ moving along x-coordinate,

𝜕2𝛹 4𝜋 2
= − 𝛹 (15)
𝜕𝑥 2 𝜆2

ℎ
From de Broglie relationship, 𝜆 = 𝑚𝑣 and substituting in equation gives

𝜕2𝛹 4𝜋 2 𝑚2 𝑣 2 8𝜋 2 𝑚𝑇𝛹
= − 𝛹 = −
𝜕𝑥 2 ℎ2 ℎ2

𝜕2𝛹 8𝜋 2 𝑚(𝐸 − 𝑉)
= − 𝛹 (16)
𝜕𝑥 2 ℎ2

𝜕2𝛹 8𝜋 2 𝑚(𝐸 − 𝑉)
= − 𝛹 (17)
𝜕𝑥 2 ℎ2

where Ψ = Ψ(x), T is kinetic energy, V is potential energy and E is total energy of the
electron (E=T+V). This is known as Schrodinger equation for particle (electron) of
mass m moving in one dimensional motion. For three dimensional motion, the equation
will be a partial differential equation with three coordinates x,y and z.

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Bonds to Bands
𝜕2𝛹 𝜕2𝛹 𝜕2𝛹 8𝜋 2 𝑚(𝐸 − 𝑉)
+ + = − 𝛹 (18)
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2 ℎ2

1.7.4 Conditions for Acceptable Wave Function

The conditions for an acceptable wave function Ψ are

1. It must be finite.

2. It must be single-valued at all points.

3. It must be continuous.

If these three conditions are obeyed then the function Ψ is called a well-behaved wave
function.

1.7.5 Motion of Quantum Mechanical Particle

The quantum mechanical particle such as electrons in atoms and molecules

can execute translational, rotational and vibrational motion. However, the common
type of motion is translational or linear when they move freely.

For linear motion of free particle which is not affected by any force or potential
barrier and free to move in limitless space, the equation (17) becomes Schrodinger
equation for free particle and is given by

𝜕 2 𝛹 8𝜋 2 𝑚𝐸
+ 𝛹=0 (19)
𝜕𝑥 2 ℎ2

Here potential energy V is a constant and assumed to be zero since the free particle is
not subjected to any potential barrier.

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Bonds to Bands
1.7.5.1 Particle in one dimensional box

Fig 1.6 Particle in one dimensional box of length L

Consider a particle is moving in a limited space like bounded electrons in

atoms and molecules serves as particle in a box model. If the limited space is a one
dimensional box of length L with infinite high walls at the two ends, the particle is not
subjected to any force inside the box where potential energy V = 0 and outside the box
it is infinity thus V = ∞.

Hence the potential energy is discontinuous (high at x=0 and x=L and inside
the box is zero), thus the Schrodinger equation should be considered inside and outside
the box separately.

The Schrodinger equation outside the box (where V = ∞) will be

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Bonds to Bands
𝜕 2 𝛹 8𝜋 2 𝑚(𝐸 − ∞)
+ 𝛹=0 (20)
𝜕𝑥 2 ℎ2

ℎ2 𝜕 2 𝛹
− + ∞𝛹 = 𝐸𝛹 (21)
8𝜋 2 𝑚 𝜕𝑥 2

The Schrodinger equation inside the box 0 ≤ x ≥ L (where V = 0)

𝜕 2 𝛹 8𝜋 2 𝑚 (𝐸 − 0)
+ 𝛹=0 (22)
𝜕𝑥 2 ℎ2

ℎ2 𝜕2𝛹
− = 𝐸𝛹 (23)
8𝜋 2 𝑚𝐸 𝜕𝑥 2

The probability of finding a particle outside the box, (i.e) Ψ2 = 0 due the large potential
energy (V = ∞) present in these regions x < 0 and x > L and thus Ψ = 0. Since Ψ must
be continuous (i.e) it cannot rise and fall suddenly, thus Ψ must be zero at x = 0 and x
= L. This is the boundary condition for this system.

The Schrodinger equation inside the box is written as

𝜕2𝛹
+ 𝑘2𝛹 = 0 (24)
𝜕𝑥 2

8𝜋 2 𝑚𝐸
𝑘2 = (25)
ℎ2

Equation (24) is satisfied by well behaved functions such as sin kx, cos kx, eikx and e-
ikx
.

Wave function and Energy of the particle

The wave function is described either in terms of real form such as sin kx and
cos kx and complex forms such as eikx and e-ikx.

The general solution of real form of wave function is given as

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Bonds to Bands
𝛹 = 𝐴 𝑠𝑖𝑛 𝑘𝑥 + 𝐵 cos 𝑘𝑥 (26)

where A and B are arbitrary constants. The values of A, B and k are determined by
applying boundary conditions to equation (26)

i. At x = 0, Ψ becomes 0

0 = 𝐴 𝑠𝑖𝑛 (𝑘. 0) + 𝐵 cos (𝑘. 0)

Thus B = 0 and hence 𝛹 = 𝐴 𝑠𝑖𝑛 𝑘𝑥 for all values of x

ii. At x = L, Ψ becomes 0

0 = 𝐴 𝑠𝑖𝑛 (𝑘. 𝐿) + 0 cos (𝑘. 𝐿)

Thus 0 = 𝐴 sin 𝑘𝐿

This expression is satisfied if either A = 0 or kL = nπ.

Case 1: If A = 0, B = 0, then Ψ becomes 0 everywhere which not acceptable.

Case 2: Thus kL = nπ or k = nπ/L where n is an integer (1,2,3…) but not zero (if n =0,
Ψ becomes 0)

The wave function and energy of the particle in one dimensional box is given as
𝑛𝜋𝑥
𝛹 = 𝐴 𝑠𝑖𝑛 (27)
𝐿

𝑘 2 ℎ2 𝑛 2 ℎ2
𝐸= = (28)
8𝜋 2 𝑚 8𝑚𝐿2

Quantization
In the energy equation (28), the terms h, m and L are constants and energy E
depends only on integer n. Thus energy is quantized (i.e) have discrete set of values

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Bonds to Bands
and the integer n is a quantum number. Hence a particle confined to move in a limited
space and its energy is quantized.

Fig 1.7 Energy levels for particle in one dimensional box

Energy levels
The Figure 1.7 shows the quantization of energy of a particle in one
dimensional box. The allowed energy levels are drawn as horizontal lines which shows
that for a value of n, energy E does not change with position x of the particle.

ℎ2
The lowest energy level E1 is not zero but 8𝑚𝐿2
(n = 1) and is also called the “zero
point energy”. The energy E depends on n2 which shows that increase in n, increases
the spacing between energy levels

∆𝐸 = 𝐸𝑛+1 − 𝐸𝑛 = [(𝑛 + 1)2 − 𝑛2 ]𝐸1 = (2𝑛 + 1)𝐸1

1
Since E is proportional to 𝐿2

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Bonds to Bands
Case 1: When the box is small the energy spacing (∆E) is greater (i.e) the quantization
is pronounced.

Case 2: When the box is wider, ∆E decreases and in limiting case of L⟶∞ (free
particle) the quantization vanishes.

1
Similarly ∆E is also proportional to 𝑚 thus for macroscopic system (large m) the energy
levels are closely spaced and there is no quantization.

Value of A

The value A is determined by the normalization of wave

function which is given by

𝐿 𝐿
𝑛𝜋𝑥
∫ 𝛹 2 𝑑𝜏 = ∫ 𝐴2 𝑠𝑖𝑛2 𝑑𝑥 = 1
0 0 𝐿

(1 − 𝑐𝑜𝑠 2𝑥)
𝑤𝑒 𝑘𝑛𝑜𝑤 𝑡ℎ𝑎𝑡 𝑠𝑖𝑛2 𝑥 =
2
𝐿
𝑛𝜋𝑥 𝐴2 𝐿 2𝑛𝜋𝑥
∫ 𝐴2 𝑠𝑖𝑛2 𝑑𝑥 = ∫ (1 − 𝑐𝑜𝑠 ) 𝑑𝑥 = 1
0 𝐿 2 0 𝐿

𝐿
𝐴2 sin 2𝑛𝜋𝑥⁄𝐿
{[𝑥]𝐿0 − [ ] }=1
2 2𝑛𝜋⁄𝐿 0

𝐴2 𝐿
=1
2

2
𝐴=√
𝐿

2 𝑛𝜋𝑥
Thus the normalized wave function is 𝛹 = √ 𝑠𝑖𝑛
𝐿 𝐿

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Bonds to Bands
1.7.5.2 Physical meaning of wave function Ψ- Probability density

In Schrodinger wave equation, Ψ is not a physically observable quantity and

does not have any direct physical meaning. However it is used to explain all the
observable physical quantities and this function is known as wave function. The
physical interpretation of square of wave function Ψ2 is a measure of the probability of
finding a particle in specified small volume of space. Ψ2 is considered if Ψ is real
function and ΨΨ* is considered when Ψ is complex and Ψ* is its complex conjugate
but the product ΨΨ* is always real.

The normalized wave function is used to calculate the probability density (i.e)
the probability of finding the particle at different points in the one dimensional box.
The probability density is given as

2 𝑛𝜋𝑥
𝛹 2 = 𝑠𝑖𝑛2
𝐿 𝐿
2
varying between 0 and . The probability of particle in a box has maximum probability
𝐿
at certain points depending on value of n and is given as

𝑏
2 𝑏 𝑛𝜋𝑥
𝑃 = ∫ 𝛹 2 𝑑𝑥 = ∫ 𝑠𝑖𝑛2 𝑑𝑥
𝑎 𝐿 𝑎 𝐿

2 𝐿
i. For n = 1, the maximum probability(𝐿) occurs at x = 2

𝐿 3𝐿
ii. For n = 2, the maximum probability occurs at x = 4 and x = 4
on both side
𝐿
of the middle point and is zero at x = and so on.
2

The probability will never be negative and these curves are always symmetric about
the reflection plane at the middle of the box.

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Bonds to Bands

Fig 1.8 Probability density curves of particle in one dimensional box for
n = 1and n = 2 energy levels

1.7.5.3 Schrodinger equation for hydrogen atom

Hydrogen atom is a two particle system which contains one electron (of mass
m and charge –e) and one proton (nucleus of mass M and charge +Ze). Consider
x1,y1,z1 and x2,y2,z2 as the Cartesian coordinates for the proton and electron respectively
which are separated by a distance r. Since the proton mass is very much greater than
electron, the reduced mass calculated will be considered as the mass of the electron.

In hydrogen atom two types of motions are involved i) translational motion of

hydrogen atom as a whole and ii) the internal motion of electron and nucleus relative
to each other. The Schrodinger equation involving these motions is

Ĥ𝛹𝑇 = 𝐸𝑇 𝛹𝑇

where Ĥ is Hamiltonian operator, ΨT = Ψ (x1,y1,z1, x2,y2,z2) and ET is the total wave

function and total energy(translational energy and internal energy) of the hydrogen

21
Bonds to Bands

Fig 1.9 Relationship between Cartesian and spherical coordinates

atom. The spatial rotation of electron around the nucleus (containing proton) can be
explained by two angular variables φ (azimuthal angle) and θ (zenith angle) and radial
distance r from the nucleus.

The Schrodinger equation of hydrogen atom is

Ĥ(𝑟, 𝜃, 𝜑)𝛹(𝑟, 𝜃, 𝜑) = 𝐸𝛹(𝑟, 𝜃, 𝜑)

22
Bonds to Bands
The hydrogen atom Hamiltonian (Ĥ = 𝑇 + 𝑉) contains kinetic energy operator T in
terms of spherical coordinates and spherically symmetrical potential energy. The
potential energy is given by

𝑍𝑒 2
𝑉=
(4𝜋𝜀0 )𝑟

The Cartesian coordinates are converted to spherical coordinates in terms of radius r

and angle φ measured between 0 to 2π and angle θ measured between 0 to π. The
relationship between x, y and z and r, θ and φ is given as

PT = OP' = r sin θ
x = OP' cos φ = r sin θ cos φ
y = OP' sin φ = r sin θ sin φ
z = OT = r cos θ

Thus the time-independent Schrodinger equation for hydrogen atom

ℎ2 1 𝜕 𝜕 1 𝜕 𝜕 1 𝜕2 𝑧𝑒 2
{ 2 [ 2 (𝑟 2 ) + 2 (𝑠𝑖𝑛𝜃 ) + 2 2 2 ]− } 𝛹 (𝑟, 𝜃, 𝜑) = 𝐸𝛹(𝑟, 𝜃, 𝜑)
8𝜋 𝑚 𝑟 𝜕𝑟 𝜕𝑟 𝑟 𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑟 𝑠𝑖𝑛 𝜃 𝜕𝜑 4𝜋𝜀0 𝑟

This equation can be separated into spherical harmonic function Y(θ,φ) and radial
function R(r) by using product wave function.

𝛹(𝑟, 𝜃, 𝜑) = 𝑅(𝑟) ∙ 𝑌(𝜃, 𝜑)

Here the spherical harmonic functions give the information about the position of
electron around the proton and the radial function R(r) tells the distance of electron
form the proton. The energy term En and the solution for R(r) and Y(θ,φ) depends only
on one quantum number n (principal quantum number). However, the other three
quantum numbers are necessary for proper description of complete wave function.

𝑚𝑒 4
𝐸𝑛 =
8𝜀02 ℎ2 𝑛2

1.8 QUANTUM NUMBERS

23
Bonds to Bands
Four quantum numbers are necessary to define an orbital. The combination of
these four quantum numbers of electrons in an atom is described by a wave function
satisfied by Schrodinger equation. The quantum numbers are used to account for the
electronic configuration of an electron in an atom and the probable position of electron
in an atom.

The quantum numbers explain the shells, subshell, orbitals and spin of electrons.
The four quantum numbers are

1. Principal quantum number (n)

The principal quantum number characterizes the principal electron shell which
decides the energy of an electron and the probable position of the electron from the
nucleus. Thus n describes the size of the orbital and energy level in which the electron
is placed. The larger the value of n, larger is the size of orbital which show that the
electron is at longer distance from the nucleus. When n = 1, it belongs to first principal
shell (ground state) and lowest energy level. When electron absorb energy it is excited
to the higher principal shells (n = 2,3,4,…). Thus n takes integral values 1,2,3…∞
except zero since when n = 0, the energy of atom becomes zero and the atom doesn’t
exists. The value of n describes the shells K, L, M, N…. in the atom.

2. Azimuthal quantum number (l)

The azimuthal quantum number or orbital quantum number characterize the shape
of the orbital and the subshell to which electron belong to. Each l value indicates
subshell which is designated as s, p, d, f. Each subshell corresponds to unique shape. It
alsodetermines the number of angular nodes of the orbital which will be equal to the
number of l values. The value of l is subshell to which electrons belong to and it
depends on n values and can have integral values from 0 to n-1. Thus

l = 0, 1, 2…. (n-1).

3. Magnetic quantum number (ml)

24
Bonds to Bands
The magnetic quantum number represents the number of orbitals and orientation
of orbitals in a subshell. The value of ml is based on the value of l and can have a total
of (2l+1) values. Thus magnetic quantum number has values as 𝑚𝑙 =
−𝑙, … ,0, … , +𝑙

Table 1.1 l and ml value for s, p, d, f subshells

Subshell l value 𝒎𝒍 value

s 0 0
p 1 -1, 0, +1
d 2 -2, -1, 0, +1, +2
f 3 -3, -2, -1, 0, +1, +2, +3

Table 1.2 Total number of orbitals in subshells

Principal Subshell corresponding to Magnetic Name of the Total number

quantum azimuthal quantum quantum subshell of orbital in
number (n) number (l) number (ml) orbital subshells

s (l =0) ml = 0 𝑠 1
ml = 0 𝑝𝑧
p (l = 1) 𝑝𝑥
ml = ±1 3
𝑝𝑦

n = 1, 2, 3, ml = 0 𝑑𝑧2
… 𝑑𝑥𝑧
ml = ±1
d (l = 2) 𝑑𝑦𝑧 5
𝑑𝑥𝑦
ml= ±2
𝑑𝑥 2 −𝑦2
ml = 0 𝑓𝑧 3

25
Bonds to Bands
Principal Subshell corresponding to Magnetic Name of the Total number
quantum azimuthal quantum quantum subshell of orbital in
number (n) number (l) number (ml) orbital subshells

𝑓𝑥𝑧 2
ml = ±1
𝑓𝑦𝑧 2
𝑓𝑥𝑦𝑧
f (l = 3) ml= ±2
𝑓𝑧(𝑥 2 −𝑦2)

𝑓𝑥(𝑥 2 −3𝑦2) 7
ml = ±3
𝑓𝑦(3𝑥 2 −𝑦2)

4. Spin quantum number (ms)

The spin quantum number refers the direction of spin of an electron in an orbital.
The direction of spin can be clockwise (ms = + ½) or anticlockwise
(ms = - ½).

1.9 ASSIGNING ELECTRONS TO ORBITALS

Three set of rules govern the filling of electrons in the orbital. They are

1. Aufbau principle

Aufbau principle states that the electrons in an atom occupy the orbital of
lowest energy before filling the higher energies. Thus electrons are filled in increasing
order of energy

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s,…..

26
Bonds to Bands

Fig 1.10 Aufbau principle

2. Pauli-Exclusion principle
It states that no two electrons in the same atom can have all the four quantum
number the same. The electrons in each orbital have three quantum numbersn, l and ml
same but the fourth quantum number ms will be different. Thus a single orbital can
accommodate a maximum of two electrons with opposite spin. The s-orbital can
accommodate 2 electrons, p-orbital can hold till 6 electrons (each 3 orbitals hold 2
electrons), the five d-orbitals can accommodate 10 electrons and seven f-orbitals can
hold 14 electrons.

27
Bonds to Bands

3. Hund’s rule

According to Hunds rule, every orbital in a subshell should be filled with

atleast one electron before pairing of electrons takes place. Further the electrons in
singly filled orbitals of subshell have the same spin.

28
Bonds to Bands
1.10 ANGULAR AND RADIAL WAVE FUNCTIONS

Thus the complete wave function of hydrogen-like atoms is given as

𝛹𝑛𝑙𝑚 (𝑟, 𝜃, 𝜑) = 𝑅𝑛𝑙 (𝑟)𝑌𝑙𝑚 (𝜃, 𝜑)

Each wave function has two parts the radial wave function Rnl(r) and angular wave
function (spherical harmonics) Ylm(θ,φ). The radial wave function depends on the
quantum numbers n and l whereas the angular wave function depends on only l and m.
The radial wave function describes the size of the atomic orbital (i.e) the distance
between the electron and nucleus. The angular wave function describes the shape of
the atomic orbital. The real forms of radial and angular wave functions and complete
wave function for s and p orbitals of hydrogen atom (Z = 1 and a0 = 1) is given below

Table 1.31 Radial, Angular wave function and complete wave function of
s and p orbitals

Quantum Radial wave Angular wave Complete wave function

numbers function function (Ψnlm)
n,l,m (Rnl) (Ylm)
n =1, l =0, m=0 𝑅10 = 2𝑒 −𝑟 1 1
𝑌00 = 𝛹1𝑠 = 𝛹100 = 𝑒 −𝑟
√4𝜋 √𝜋
n =2, l =0, m=0 1 −𝑟⁄ 1 1 −𝑟⁄
𝑅20 = (2 − 𝑟) 𝑒 2 𝑌00 = 𝛹2𝑠 = 𝛹200 = (2 − 𝑟)𝑒 2
2√2 √4𝜋 4√2𝜋
n =2, l =1, m=+1 1 −𝑟⁄ 1 −𝑟⁄
𝑅21 = 𝑟𝑒 2 3 𝛹2𝑝𝑥 = 𝛹21+1 = 𝑟𝑒 2
2√6 𝑌1 +1 = √ 𝑠𝑖𝑛𝜃 𝑐𝑜𝑠𝜑 4√2𝜋
4𝜋
𝑠𝑖𝑛𝜃 𝑐𝑜𝑠𝜑
n =2, l =1, m=-1 1 −𝑟⁄ 1 −𝑟⁄
𝑅21 = 𝑟𝑒 2 3 𝛹2𝑝𝑦 = 𝛹21−1 = 𝑟𝑒 2
2√6 𝑌1 −1 = √ 𝑠𝑖𝑛𝜃 𝑠𝑖𝑛𝜑 4√2𝜋
4𝜋
𝑠𝑖𝑛𝜃 𝑠𝑖𝑛𝜑
n =2, l =1, m= 0 1 −𝑟⁄ 1 −𝑟⁄
𝑅21 = 𝑟𝑒 2 3 𝛹2𝑝𝑧 = 𝛹210 = 𝑟𝑒 2
2√6 𝑌10 = √ 𝑐𝑜𝑠 𝜃 4√2𝜋
4𝜋
𝑐𝑜𝑠 𝜃

29
Bonds to Bands
1.11 WAVE FUNCTION OF ATOMIC ORBITALS AND
ORBITAL SHAPES

The wave function Ψ(r,θ,φ) of hydrogen atom is known as atomic orbitals.

Atomic orbital is a wave function that explains the behavior of an electron in atom or
region of space. Orbital of different systems varies only with nuclear charge Z. The
probability of finding an electron in atom is described by Ψ2 (square of wave function
of atomic orbital).

1.11.1 Orbital Shapes

Each orbital is represented by a number and a letter where the number
(1, 2, 3, …) indicates the energy level of the electron in the atom and letter (s, p, d, f)
denotes the shape of the orbital. From the solution of Schrodinger wave equation,
diagrammatic representation of shapes of atomic orbitals is drawn using the boundary
surface diagrams.
A boundary surface diagram is a boundary surface for an orbital represented in a
space where the value of probability density Ψ2 is a constant.
1. s-orbital
Boundary surface diagram of s-orbital is spherical with nucleus at the center. All
the s-orbitals 1s, 2s, 3s,… are spherically symmetrical but their size and energy
increases with increase in principal quantum number (n) values (1s< 2s< 3s…..).

30
Bonds to Bands

Fig 1.11 Boundary surface diagram of s-orbital

2. p-orbital

Boundary surface diagram of p-orbital show two lobes on either side of plane
passing through the center of the nucleus called nodal plane that bisects the two lobes.
Unlike s-orbital, the p-orbital has three orientations that are designated as px, py and pz
which lie on x, y, z axes which are mutually perpendicular to each other.

These three p-orbitals have same energy, size and shape. The size and energy of
the p-orbital increase with increase in n values (2p< 3p< 4p…).

31
Bonds to Bands

Fig 1.12 Nodal planes and Boundary surface diagram of p- orbitals

3. d-orbital

Boundary surface diagram of four of the five d-orbitals (𝑑𝑥𝑧 , 𝑑𝑦𝑧 , 𝑑𝑥𝑦 , 𝑑𝑥 2 −𝑦2 )
consists of four lobes arranged in a plane which is intersected by two perpendicular
nodal planes.

32
Bonds to Bands

Fig 1.13Nodal planes and Boundary surface diagram of d-orbitals

The fifth d-orbital 𝑑𝑧2 show two lobes in z-axis and a doughtnut of electron density
in the xy plane. However the energy of all five d-orbitals is same. The size and energy
of d-orbital increases with increase in n values (3d< 4d< 5d…).

33
Bonds to Bands
4. f-orbital

When n = 4 and l = 3, the subshell consists of seven f-orbitals. The boundary surface
diagrams show that each f-orbital has three nodal surfaces and thus their shapes are
complex and difficult to represent by simple diagram.

1.12 THEORY OF BOND FORMATION

Two theories which explain the bond formation are

1. Valence bond theory

2. Molecular orbital theory

1.12.1 Valence Bond Theory (VB Theory)

Valence bond theory explains the formation of covalent bonds in molecules

based on the number of valence electrons and does not consider the other electrons in
the atom. The VB theory is based on the concept of atomic orbital overlap. Atomic
orbital overlap is the interaction of two atomic orbitals of two atoms followed by
sharing of electrons of atoms.

Salient features of Valence bond theory

1. According to this theory covalent bonds are formed between atoms that are
sufficiently closer andcan overlap their atomic orbitals.
2. Covalent bond is formed by a pair of electrons shared by two atoms.
3. Lone pair of electrons does not involve in bond formation.

34
Bonds to Bands
Formation of covalent bond in H2 molecule

Consider two hydrogen atoms HA and HB which are far away from each other.
Each hydrogen atom contains one electron in 1s atomic orbital. When the two hydrogen
atoms come closer there is overlap of these two 1s atomic orbitals resulting in the
covalent bonding. Now the electron in HA can revolve around nuclei of HB and vice
versa. Thus after bond formation the two electrons lose their identity and cannot
distinguish which electron belong to HA and HB. The two electrons can move into
orbitals of two atoms. These electrons are equally shared between the orbitals and form
a covalent bond.

❖ Pairing of electrons results in decrease of energy of the system

❖ This leads to the formation of bond between the atoms which produce a
molecule
❖ It increases the stability of the system, thus a molecule of hydrogen is more
stable than two hydrogen atoms
❖ The atoms involved in the bond formation attain stable electronic
configuration (Noble gas configuration)
❖ A pair of electrons shared by two atoms creates a covalent bond

❖ Bond pair and Lone pair:

A pair of electrons between two bonded atoms constituting the bond is

known as bond pair and pair of electrons which does not involve in bonding is
known as lone pair.

35
Bonds to Bands
❖ Atom may contain non-bonding electron pair (i.e) a pair of valence electrons
present on a bonded atom which does not involve in bonding. For example,
NH3 contains three bond pair and one non-bonding electron pair (lone pair)
and water has two bond pair and two lone pairs.

VB theory to some molecules

1. HF: In HF molecule, singly filled 1s orbital of H atom overlap with singly

filled 2p orbital of F to form H – F covalent bond. The three lone pair of
electrons remains as non-bonding electron pair on F atom.

2. H2O: In H2O molecule, O atom contains two singly filled 2p orbitals which
overlap with singly filled 1s orbital of each H atom to form two O – H bonds.
Two lone pair of electrons is present as non-bonding electron pair on O atom.

3. NH3: In NH3 molecule, N atom contains three singly filled 2p orbitals which
overlap with singly filled 1s orbital of each H atom to form three N – H bonds.
One lone pair of electrons is present as non-bonding electron pair on N atom.

Types of orbital overlap

36
Bonds to Bands
Depending on the types of atomic orbital involve in bonding, different types of
bonds are possible.

1. σ bond: A covalent bond formed by end-to-end or head-to-head overlap of

atomic orbitals of two atoms such as overlap of s – s, s – px, px – px atomic
orbitals is called a σ bond.
2. π bond: When p orbitals of two atoms approach along and have a lateral
overlap such as overlap of pz – pz or py – py atomic orbitals is called a π bond.

Success of VB theory

1. It successfully explains the covalent bond formation in molecules by using

concept of atomic orbital overlap.
2. According to this theory electron pairing results in decrease of energy of the
system which contributes to stability of the system.
3. It also explains the geometries of many covalent molecules.
4. It clearly depicts the strength of σ bond and π bond.
5. Application of VB theory has lead to development of stereochemistry of
carbon compounds.

Limitations of VB theory

1. This theory ignores the electrons other than the valence electrons.
2. It does not explain the partial ionic character of bonds.
3. It does not explain the bond formation in complex multi-atom molecules.
4. It cannot account for coordinate bond in which one atom donates both the
electrons required for bond formation.
5. It does not explain the bond formation in molecules like H2+ and He2+ which
involves sharing of single electron.

37
Bonds to Bands
1.12.2 Linear Combination of Atomic Orbitals – Molecular Orbitals (LCAO-
MO)

In the VB theory even after the formation of the molecule, the atomic orbitals
remain as such and retain their identity with respect to their atoms.

In the MO theory, after the formation of the molecule, the valence electrons
lose their identity and they no longer belong to individual atoms but belong to molecule
as a whole.

Salient features of Molecular Orbital theory

1. According to MO theory the atomic orbitals (AO) of the atoms combine to

form new orbitals known as molecular orbitals (MO).
2. Molecular orbitals are described by wave functions based on quantum
chemistry.
3. Overlapping of two AO results in formation of two MO (i.e) one bonding MO
and one antibonding MO.

Wave function

1. Every atom can possess full set of s,p,d,f orbitals but not all of them will have
electrons
2. The space where there is more probability of finding electrons is called atomic
orbital.
3. The representation of AO is called electron probability density diagram which
show the most probable distribution of electron cloud around the nuclei.
4. Each AO is described by a wave function.
5. For example wave function of 1s and 2p orbital is shown below where r is the
distance between electron and nucleus.

38
Bonds to Bands

Fig 1.14 wave function of 1s orbital and 2porbital

❖ The wave function of the 1s orbital is always positive sign (above the
reference axis)
❖ The wave function of 2p orbital is sometimes positive sign (above the axis)
and sometimes negative (below the axis). Thus changes sign from positive
to negative.
❖ The above fact is represented as electron probability density diagram (AO)
with + or – sign. These two sign indicates the relative probabilities and –
sign does not show that the probability is negative.
❖ The probability density diagram describes the shape of the atomic orbital.
Shapes of 1s orbital and 2pz orbital are shown below.

39
Bonds to Bands

Fig 1.15 Probability density diagram of 1s orbital and 2p orbital

Combination of wave function: Bonding and Antibonding molecular orbitals

Two waves can overlap in two different ways to form bonding molecular
orbital or antibonding molecular orbital. The overlap of the positive part of one AO
with positive part of another AO and negative part of one AO with negative part of
another AO reinforces and produce a larger wave known as bonding molecular orbital.
Similarly the overlap of the positive of one AO with the negative part of another AO
results in destruction of wave and produces an antibonding molecular orbital.

1.12.2.1 LCAO – MO of H2

Molecular orbital is described by wave function similar to atomic orbital. The

wave function of MO is obtained by Linear combination of atomic orbitals method.
This concept can be explained by considering hydrogen molecule H2. Hydrogen
molecule has two hydrogen atoms HA and HB whose atomic orbitals are described by
wave function φA and φB. These two atomic orbitals overlap (i.e) φA ± φB and
produce a new wave function known as molecular orbital. Such algebraic sum of
functions is called as linear combination.

40
Bonds to Bands

Fig 1.16 Formation of bonding and antibonding molecular orbital

byreinforcement and destruction of two AO waves

The two normalized LCAO wave functions are

𝛹𝑏 = 𝑁𝑏 (𝜑𝐴 + 𝜑𝐵 ) (1)

𝛹𝑎 = 𝑁𝑎 (𝜑𝐴 − 𝜑𝐵 ) (2)

41
Bonds to Bands
WhereΨb and Ψa are wave function, Nband Na are Normalization constant of bonding
and antibonding molecular orbitals respectively. The numerical value of Nband Na was
calculated to be 0.71 (~√½). The energy of LCAO-MO’s Ψb and Ψa is represented as
Eb and Eaand is given as

∫ 𝛹𝑏 Ĥ 𝛹𝑏 𝑑𝜏 𝑁𝑏2 ∫(𝜑𝐴 + 𝜑𝐵 ) Ĥ (𝜑𝐴 + 𝜑𝐵 )

𝐸𝑏 = = (3)
𝛹𝑏 𝛹𝑏 𝑑𝜏 1

𝐸𝑏 = 𝑁𝑏2 (∫ 𝜑𝐴 Ĥ 𝜑𝐴 𝑑𝜏 + ∫ 𝜑𝐴 Ĥ 𝜑𝐵 𝑑𝜏 + 𝜑𝐵 Ĥ 𝜑𝐴 𝑑𝜏 + ∫ 𝜑𝐵 Ĥ 𝜑𝐵 𝑑𝜏) (4)

Where Ĥ is the Hamiltonian operator (total energy operator). Substituting the integrals
with symbols

𝑄𝐴 = ∫ 𝜑𝐴 Ĥ 𝜑𝐴 𝑑𝜏 (5)

𝑄𝐵 = ∫ 𝜑𝐵 Ĥ 𝜑𝐵 𝑑𝜏 (6)

𝛽 = ∫ 𝜑𝐴 Ĥ 𝜑𝐵 𝑑𝜏 = ∫ 𝜑𝐵 Ĥ 𝜑𝐴 𝑑𝜏 (7)

Since both the atoms A and B are H atom, QA = QB = Q and the energy equation (4)
becomes

𝐸𝑏 = 2𝑁𝑏2 (𝑄 + 𝛽) (8)

Similarly

𝐸𝑎 = 2𝑁𝑎2 (𝑄 − 𝛽) (9)

Here integral Q represents the energy of an electron in the orbital φA or φB that is equal
to the ground state energy of hydrogen atom. The integral β represents the energy of
interaction between the orbitals φA and φB. It is called exchange integral and is
inherently negative. Thus an electron occupying bonding MO, Ψb is more stable and

42
Bonds to Bands
an electron in Ψa is less stable than electron in a pure atomic orbital, φA or φB. The
actual energy of stabilization and destabilization is obtained by substituting
Normalization constant Na and Nb (Na = Nb = √½) in equation (8) and (9).

𝐸𝑏 = (𝑄 + 𝛽) (10)

𝐸𝑎 = (𝑄 − 𝛽) (11)

This is depicted in the energy level diagram as

Fig 1.17 Energy level diagram for formation of bonding and antibonding
MOof H2molecule

43
Bonds to Bands
As the bonding and antibonding orbitals are formed, the AO overlap, energy
changes occur. The formation of the bonding MO (Ψb) decreases the energy and that
of antibonding MO (Ψa) increases the energy.

• The energy of the bonding MOis lower than that of antibonding MO.

• The energy difference between AO and bonding MO is called stabilization

energy and it is denoted as β.

• The energy difference between AO and antibonding MO is denoted as β.

• Each MO can accommodate two electrons with opposite spins similar to AO.

• The energy of each electron is decreased by β and hence the total reduction in
energy of the system is 2β. This denotes the bond energy.

• This reduction in energy is the driving force for bond formation.

• When two AO of H atoms combine, it forms lower energy bonding MO which

is designated as σ 1s and higher energy antibonding MO which is designated
as σ* 1s.
• The two electrons each from AO of H atom occupy the lower energy bonding
MO with opposite spins.
• In homonuclear diatomic molecule such as H2 molecule, each H atom has an
electron and they occupy the lower energy MO σ1s. Hence the MO
configuration for H2 is σ1s2.

44
Bonds to Bands

Fig 1.18 Combination of s – s atomic orbitals to form bonding

andantibonding molecular orbitals

Fig 1.19 Combination of s – p atomic orbitals to form bonding

andantibonding molecular orbitals

45
Bonds to Bands

Fig 1.20 Combination of px – px atomic orbitals to form bonding

andantibonding molecular orbitals

Fig 1.21 Combination of py– pyatomic orbitals to form bonding

andantibonding molecular orbitals
46
Bonds to Bands
1.13 BAND THEORY

Band theory is a quantum model which gives an insight about the possible
energies of electrons in the solids in order to understand the electrical and optical
properties of solids. It is the molecular orbital theory of covalent bands extended to
solids. A single atom has discrete energy states or energy levels of electrons, however
in the case of assembly of atoms, situation is somewhat different. Like when two atoms
come closer, their atomic orbitals get overlapped to form new orbits called molecular
orbitals (bonding and antibonding).When large number of atoms are in close
association as in case of solids, the discrete nature of energy levels of atoms vanishes
and there are formation of large number of energy levels having close energy
differences, which in the other sense can be called a band of energy levels or energy
bands.

L Li2 Li3 Li4 Li5 LiN

i
(a) (b) (c) (d) (e) (f
)
llustration of band theory: (a) single Li-atom with one 2s-valence electron, (b) Li2
with two M.O., one filled and one vacant, (c) Li3 with three M.O., (d) Li4 with four
M.O., (e) Li9 with nine M.O., half-filled, (f) LiN with a band of N M.O.

47
Bonds to Bands
In order to understand band theory of solids, let us imagine the construction of
lithium metal by adding Li-atoms one at a time, forming Li2 then Li3, Li4, Li5 and so
on, until we have LiN, where N is a very large number of the order of 1020.

Electrons in the solids having allowed energies belong to the allowed energy
bands. The allowed energy bands can be separated by forbidden band to which the
electron energy in the solid does not belong. The allowed energy bands are of two types
called valence band and conduction band. In a solid, valence band and conduction band
can be separated by a forbidden band as incase of semiconductors and insulators.
Hence the solids have three types of energy bands which are valence band, forbidden
band and conduction band.

Salient features of band theory:

1. Solids are made up of giant molecules, in which a very large number

of spherical atoms are arranged in a regular close-packed pattern in the
form of crystals.
2. When the atoms are brought together in solids, the atomic orbitals of the
valence shells ‘interact’ forming molecular orbitals.
3. During interaction between these atoms, they influence each other and
constitute one single system of electrons while the inner shells remain
intact and are not affected.
4. The individual energies within an energy band are so-close together and
considered to be continuous. Consequently, an electron in a solid crystal
can occupy any of these large number of energy level, within the band.
Thus, a band is a group of infinitesimally energy levels in a solid/crystal.

48
Bonds to Bands

Conduction
Unfilled band
Bands

Band gap

Valence
Filled band
Bands

Fig 1.22 Energy bands in solids

Depending upon the composition of a solid/crystal, the bands are of three types.

1. Valence band:

Valence band is the band of energy levels occupied by the valence electrons. It is
lowest in energy among three types of bands. Valence band is generally fully filled in
insulators, however incase of conductors valence band is partially filled by electrons.
This band is below the forbidden band and valence electrons are present in this band.
In conductors valence electrons are free to move in this band and are easily transferred
into the conduction band without giving any external energy.
49
Bonds to Bands
2. Conduction band:

The next permitted band, above the valence band, is called the conduction band
and the electrons occupying this band are called conduction electrons. It is the band of
orbitals in which electrons are present which have been jumped from the valence band.
It is higher in energy than the valence band and forbidden band. Electrons in this band
have enough energy to move freely and if some external force is applied in the form
potential difference across the ends of solid, electrons flow in a particular direction
which we called the flow of charge or electric current. This band is responsible for the
conduction of electricity.

Overlap

Conduction
band
Electron energy

------------------------
Band
Fermi level
gap

Valence band

Metal Semi Conductor Insulator

Fig 1.23 Valence, conduction and forbidden (band gap) in solids

On the basis of presence of forbidden band gap energy and band gap size, solids
can be distinguished into three types namely conductors, insulators and semi-
conductors.
50
Bonds to Bands
A. Conductors:

In conductors there is zero band gap energy. Valence band and conduction band
are overlapped. So the electrons in the valence band can easily move into conduction
band. Presence of large number of free electrons in the conduction band results in the
flow of electric current. Metals have zero band gap energy. So the electrons in the
valence band are free to move into the conduction band without gaining any additional
energy and hence they are good conductors of electricity.

B. Insulators:

Insulators have large band gap energy and band gap size. It is difficult for an
electron from a valence band to gain energy and move into conduction band. Absence
of free electrons in the conduction band of insulators restricts the flow of electric
current in insulators. So the insulators are poor conductors of electricity. The
conductivity of insulators is 24 orders of magnitude less than conductors.

C. Semiconductors:

Semiconductors have small band gap energy and band gap width. The band gap in
semiconductors is approximately 1 eV and it is possible for an electron in the
conduction band to gain this small amount of energy and enter into conduction band to
have some conductivity. Conductivity of semiconductors is between that of insulators
and conductors which is about 4-16 orders of magnitude less than conductors. It is
further possible for the semiconductors to decrease or tailor this band gap energy,
which find its useful applications in electronics and photoelectronics. Semiconductors
are being used in the electronic devices such as radios, computers, mobile phones,
televisions, automobiles, amplifiers. Semiconductors are being used in the formation
of integrated circuits, transistors, diodes, photovoltaic cells etc.

51
Bonds to Bands
Examples of semiconductors include silicon, germanium, antimony, boron,
tellurium, selenium etc.

Type of semiconductors

Semiconductors are classified into two types as:

i. Intrinsic semiconductors.

Intrinsic semiconductors are extremely pure (above 99.9999% pure) elements like
silicon, germanium and selenium, having four valence electrons in their atoms and
their forbidden gap energy is about 1 eV. These metals have crystalline structures, in
which each atom forms four covalent bonds by sharing with four neighbouring atoms.
In such semiconductors, the energy gap is so small (about 1 eV) that even at ordinary
temperature, there are many valence electrons, which possess sufficient energy to jump
across the forbidden gap to conduction band. Intrinsic semiconductors are also called
undoped semiconductors.

ii. Extrinsic semiconductors.

Extrinsic semiconductor are basically intrinsic semiconductors, whose conducting

properties have been improved by adding extremely small amounts of specific
substitutional impurities called doping agent or dopants. The addition of doping agent
reduces the energy gap (Eg), thereby allowing more electrons to flow from valence
band to the empty conduction band. Usually, 1 part of doping agent is added to 106
parts of parent element (Si, Ge, etc.). By appropriate doping, the conductivity of an
intrinsic semiconductor may be increased by 10,000 times. Dopants added to the
extrinsic semiconductor gives desired electrical and optical properties to the
semiconductor.

Based on the nature of the doping agent added, the extrinsic semiconductors
are of following two classes:
52
Bonds to Bands
Doping

Doping is a process of adding an impurity to the semiconductor in order to

modulate the properties and obtain the desired electrical, optical and structural
properties of the semiconductor. The impurity added to the semiconductor is called
dopant.

Ge Ge Ge

Ge Ge Ge

Ge Ge Ge

Ge Germanium nucleus +28 electrons

Valance electrons
Covalent bond

Fig 1.24 Intrinsic semiconductor

53
Bonds to Bands

Surplus Hole
electron

Pentavalent Trivalent
impurity atom impurity
(donor) Atom
(acceptor)

Fig 1.25 Extrinsic semiconductor

Dopants are of two types which include n-type and p-type dopants. Generally
doping is done to increase the conductivity of semiconductors. Doping increases the
charge carriers that results in the increased electrical conductivity of semiconductor.
Higher the increase in the number of charge carriers in the semiconductor higher is its
electrical conductivity.

Doping atoms occupy the lattice positions of the semiconductor. They increase
the number of charge carriers of the semiconductor in the form of electrons and holes.

Electrons are negatively charged but the holes attain the positive charge.
Generally group III and group V elements of periodic table are extensively used as
dopants.

54
Bonds to Bands
Types of Extrinsic semiconductor:

1. n-type semiconductor :

It is an excess negatively charged electrons containing semiconductor and obtained

by adding extremely small quantity of a pentavalent element impurity like phosphorus,
arsenic or antimony to pure intrinsic semiconductor crystal lattice like silicon,
germanium, tellurium etc.

Si Si Si Si Si
e-
Si P Si Si Si

Si Si Si Si Si

Si Si Si Si Si

Fig 1.26 n-type semiconductor

Conduction Process:The doping atom forms four covalent bonds with the
surrounding four Si atoms of intrinsic semiconductor with the help of four of its five
valence electrons, while the fifth excess electron remains loosely bound to the donor
atom. This loosely bound excess electron is easily excited from the valence band to the
conduction band, when an electric field is applied. Thus, conduction is due to
movement of excess electrons present in an n-type semiconductor. In other words, the
electrical conductivity of an n-type semiconductor is dependent only on the number of
55
Bonds to Bands
free or excess electrons present in the conduction band. This results in the increase of
negatively charged electrons and hence n-type semiconductor is formed. Here n stands
for negative charge or sign. Increase of charge carriers in the form of negatively
charged electrons increases the electrical conductivity of semiconductor.

2. p-type semiconductor :

It is an excess positively charged holes containing semiconductor and is obtained

by adding an extremely small quantity of trivalent element like boron, aluminum to the
pure intrinsic semiconductor crystal lattice like silicon, germanium, etc.

Conduction process: All the three valence electrons present in the trivalent doping
agent (an acceptor atom) form three covalent bonds with the surrounding three of the
four atoms, thereby one bond in one of the four surrounding Ge atoms is left
incomplete. This gives rise to a positive hole. The positive hole so formed in the crystal
lattice conduct current, when electric field is applied. During this type of conduction
process, a hole travels to an adjacent atom by acquiring an electron and re-establishing
a new covalent bond, by breaking an existing covalent bond in the adjacent atom and
creating a new hole of it. In this way, holes are filled by electrons from one atom to
another and creating new holes in sequence in the crystal lattice.

The movement of holes through the crystal of a p-type extrinsic semiconductor

is nothing but movement of a positive electric charge. Holes carry the current by
accepting electrons and move in the opposite direction to that of electrons during the
flow of electric current.

Thus, in such a semiconductor, the positively charged holes are in excess and
the only charge-carriers during conduction.

56
Bonds to Bands

Si Si Si Si Si

Si B Si Si Si

Si Si Si Si Si

Si Si Si Si Si

Fig 1.27 p-type semiconductor

Role of Arsenic doping on Silicon:

Arsenic is a group V element or pentavalent. It is doped with silicon

semiconductor to form n-type semiconductor. Arsenic atom enters into lattice position
of silicon atom and bonds covalently with four silicon atoms. The fifth electron of
arsenic is free to move in the semiconductor which results in the increase of charge
carriers and hence conductivity of semiconductor. Not only with silicon, arsenic can
also be doped with other semiconductors.

57
Bonds to Bands
Arsenic bonded electron Arsenic unbonded electron

S S S S
i i i i
e-

S As S S
i i i

S S S S
i i i i

Fig 1.28 Doping of arsenic with silicon

Role of Gallium doping on Silicon:

Gallium belongs to third group of periodic table. It is trivalent element. It can

be doped with silicon to form p-type semiconductor. It has only three valence electrons
in its outer most shell. In the lattice structure, it is surrounded by four silicon atoms
and hence creating electron deficient sites called holes. These holes are ready to accept
the electrons and increase the electrical conductivity of semiconductor. Germanium
can also be doped with gallium to form p-type semiconductor.

58
Bonds to Bands
1.14 SUPERCONDUCTORS

Ordinary metals conduct electricity and their specific conductivity is around

106 ohm-1cm-1. It has been found that for a number of metals and alloys, the electrical
resistance disappears abruptly and completely at temperatures, a few degrees above
absolute zero. Low temperature research has led to the discovery of an amazing
phenomenon of superconductivity.

S S S
i i i
Hole

S Ga S
i i

S S S
i i i
Fig 1.29 Doping of gallium with silicon

Superconductors are materials which conduct electricity without any

electrical resistance. The maximum temperature, in which a superconducting material
exhibits superconductivity, is called its critical temperature (Tc). Materials in
superconducting state become diamagnetic and are repelled by magnets. The
phenomenon of superconductivity was first observed by Heiki Kammerlingh Onnes, a
Dutch physicist in 1913 and found that mercury became superconducting at 4K (at
boiling point of liquid helium).
59
Bonds to Bands
having composition YBa2Cu3O7-y and exhibits superconductivity well above 77K. The
structure of 1: 2: 3 compound is similar to mineral perovskite (CaTiO3) structure.

Applications of superconductivity:

The phenomenon of superconductivity has many applications such as:

1. Superconducting magnets capable of generating high fields with low power

consumptions are being employed in scientific tests and research equipments.
2. They are also used for magnetic resonance imaging (MRI) in the medical field
as a diagnostic tool.
3. It is used as a magnet for high-energy particle accelerators.
4. It is used as a memory or storage elements in computers.
5. It is used in high-speed magnetically levigated trains.
6. It is used in high-speed switching and signal transmission for computers.

Solved Problems

1. When a radiation of wavelength 500 nm strikes a metal surface, electrons are

emitted from the surface of a metal. The kinetic energy for one electron emitted
from the metal is 1  10-19J. Calculate the minimum energy required to remove
an electron from a metal (binding energy).

Solution:

Wavelength λ =500 nm

Incident radiation energy

ℎ𝑐 6.626 × 10−34 × 3 × 108

𝐸 = ℎ𝜈 = = = 3.975 × 10−19 𝐽
𝜆 500 × 10−9

62
Bonds to Bands
1
ℎ𝜈 = 𝜔 + 𝑚𝓋 2
2

The minimum energy required to remove an electron from a metal is

1
𝜔 = ℎ𝜈 − 𝑚𝓋 2 = (3.975 × 10−19 ) − (1 × 10−19 ) = 2.975 × 10−19 𝐽
2

2. Calculate the wavelength of an electron having velocity 6  106 ms-1and mass

9.1  10-31 Kg.

Solution: The wavelength of an electron

ℎ ℎ 6.626 × 10−34 𝐽𝑠
𝜆= = =
𝑝 𝑚𝑣 (9.1 × 10−31 𝐾𝑔) × (6 × 106 𝑚𝑠 −1 )

= 1.2 × 10−9 𝑚 𝑜𝑟 1.2 𝑛𝑚

3. Calculate the uncertainty in position for a ball of mass 0.2 Kg moving with a
speed of 10 ms-1is measured at an accuracy of 1%.

Solution: The momentum of the ball is given by

𝑝 = 𝑚𝓋 = 0.2 𝐾𝑔 × 10𝑚𝑠 −1 = 2 𝐾𝑔. 𝑚𝑠 −1

Thus uncertainty in momentum is calculated from momentum and % of

accuracy

∆𝑝 = 2 × 0.01 = 0.02 𝐾𝑔. 𝑚𝑠 −1

ℎ 6.626 × 10−34 𝐽𝑠
∆𝑥 = = = 3.31 × 10−32 𝑚 ∵ 1 𝐽 = 1 𝐾𝑔. 𝑚2
∆𝑝 0.02 𝐾𝑔. 𝑚𝑠 −1

63
Bonds to Bands
4. Calculate the zero point energy of an electron of mass 9.1 x 10-31Kg in one
dimensional box of length 1Å.

Solution: The energy of electron in one dimensional box is

𝑛2 ℎ2 𝑛2 × (6.626 × 10−34 𝐽𝑠)2

𝐸= =
8𝑚𝐿2 8 × (9.1 × 10−31 𝐾𝑔) × (1 × 10−10 𝑚)2

= 𝑛2 × 4.16 × 10−20 𝐽𝑠 2

The zero point energy is the lowest energy level or first energy level

𝐸1 = 12 × 4.18 × 10−20 𝐽𝑠 2

5. Calculate the energy difference between E4 and E3 for an electron in a one

dimensional box of length 12Å.

Solution: The energy of electron in one dimensional box is

𝑛 2 ℎ2 𝑛2 × (6.626 × 10−34 𝐽𝑠)2

𝐸= = = 𝑛2 × 4.16 × 10−20 𝐽𝑠 2
8𝑚𝐿2 8 × (9.1 × 10−31 𝐾𝑔) × (12 × 10−10 𝑚)2

The electron in lowest energy level or first energy level

𝐸1 = 12 × 4.18 × 10−20 𝐽𝑠 2

∆𝐸 = 𝐸4 − 𝐸3 = (2𝑛 + 1)𝐸1 = (6 + 1) × 4.16 × 10−20

= 2.912 × 10−20 𝐽𝑠 2 𝑜𝑟 𝑊𝑎𝑡𝑡 𝑠𝑒𝑐𝑜𝑛𝑑

6. Determine the value of A in wave function of particle in one dimensional box

of length L and find out the normalized wave function of it by normalization
method.

Solution: The value A is determined by the normalization of wave function

which is given by

64
Bonds to Bands
𝐿 𝐿
𝑛𝜋𝑥
∫ 𝛹 2 𝑑𝜏 = ∫ 𝐴2 𝑠𝑖𝑛2 𝑑𝑥 = 1
0 0 𝐿

(1 − 𝑐𝑜𝑠 2𝑥)
𝑤𝑒 𝑘𝑛𝑜𝑤 𝑡ℎ𝑎𝑡 𝑠𝑖𝑛2 𝑥 =
2
𝐿
𝑛𝜋𝑥 𝐴2 𝐿 2𝑛𝜋𝑥
∫ 𝐴2 𝑠𝑖𝑛2 𝑑𝑥 = ∫ (1 − 𝑐𝑜𝑠 ) 𝑑𝑥 = 1
0 𝐿 2 0 𝐿

𝐿
𝐴2 sin 2𝑛𝜋𝑥⁄𝐿
{[𝑥]𝐿0 − [ ] }=1
2 2𝑛𝜋⁄𝐿 0

𝐴2 𝐿
=1
2

2
𝐴=√
𝐿

2 𝑛𝜋𝑥
Thus the normalized wave function is 𝛹 = √ 𝑠𝑖𝑛
𝐿 𝐿

Questions:

Part-A

1. What is a black body radiation?

2. Recall Rayleigh-Jean’s Law.

3. What is Planck’s law of radiation?

4. Summarize the photoelectric effect.

65
Bonds to Bands
5. How is kinetic energy of emitted electrons related to frequency and intensity
of incident light?

6. Tell de Broglie’s hypothesis.

7. Define Heisenberg’s Uncertainty principle.

8. What are the conditions for acceptable wave functions?

9. Define zero point energy for 1D box.

10. What happens to spacing of energy levels when length of one dimensional box
increases?

11. Outline the wave function and energy for a particle in 1D box.

12. What is probability density?

13. List out the types of quantum numbers.

14. Define Aufbau principle.

15. Explain Pauli’s exclusion principle.

16. Define Hund’s rule.

17. Draw the structure of p-orbitals.

18. Determine the number of orbitals in d subshell.

19. Compare the bonding and antibonding molecular orbitals.

20. Explain conductors, semiconductors and insulators with a neat diagram.

21. What are super conductors? Give example.

22. Differentiate between n-type and p-type semiconductor.

23. List out the properties of superconductors.

24. List out the applications of superconductors.

25. Define Meissner effect.

66
Bonds to Bands
Part-B

1. Elaborate the LCAO-MO method in the formation of hydrogen molecule.

2. Formulate the Schrodinger wave equation for a particle in one dimensional
box and determine the wave function and energy of the particle.
3. Determine the value of A in the wave function of particle in 1D box by
Normalization method.
4. Outline the time-independent Schrodinger equation of hydrogen atom using φ
and θ.
5. Explain the various shapes of atomic orbitals with neat sketch.
6. Summarize the significance of four quantum numbers.
7. Explain band theory of solids with neat diagram.
8. Discuss the various types of semiconductors with suitable examples.
9. Explain the role of doping of arsenic and gallium on silicon with neat diagram.
10. Write a note on superconductor with suitable example.

References

1. A.K.Chandra, Introductory Quantum Chemistry, Tata McGraw-Hill, 4th

edition, 1994.

2. R. K. Prasad, Quantum Chemistry, New Age International (P) Limited

Publishers, 4th edition, 2010.

3. Ira N. Levine, Quantum chemistry, 7th Edition, 2013.

4. R. Gopalan, Text book of Inorganic Chemistry, University press (India)

Private Limited, 2012.

5. P.C. Jain, Monica Jain, Engineering Chemistry, DhanpatRai Publishing

Company, 16th edition, 2013.

67