Molecular Spectros

CHM 307
ATOMIC AND MOLECULAR STRUCTURE AND SYMMETRY
Course Team: Dr. N.A.A. Babarinde (Developer/Writer)-

Olabisi Onabanjo University Ago-Iwoye,
Ogun State
Prof. Nnabuk Okon Eddy (Course
Revised/Reviewer)- Department of Pure and
Industrial Chemistry University of Nigeria,
Nsukka, writer
NATIONAL OPEN UNIVERSITY OF NIGERIA

CHM 307 COURSE GUIDE
National Open University of Nigeria

Headquarters
Plot 91, Cadastral Zone,
Nnamdi Azikiwe Expressway,
Jabi - Abuja
Email: [email protected]
URL: www.nou.edu.ng
Published by
National Open University of Nigeria
Revised in 2019
Printed 2021
ISBN: 978-978-058-037-7
ii
CONTENTS PAGE
Introduction…………………………………………. iv
Course Description…………………………………. iv
What you will Learn in this Course………………… v
Course Aims………………………………………… v
Course Objectives…………………………………… v
Working through this Course……………………….. vi
Study Units…………………………………………… vi
Course Materials…………………………………….. vii
Textbooks and References…………………………... vii
Assessment…………………………………………… viii
iii
INTRODUCTIONS
Theories of molecular structure can be generally divided into classical

and quantum theories. The classical theory considers atom as a particle
in having a well-defined geometric in space, while quantum theory
attempts to explain molecular structure on the bases of the Schrodinger
equation. The oldest of these theories is the classical theory, which was
able to propose that all atoms have electron that revolves in an orbit,
having a characteristic levels and energy. Several scientists were deeply
involved in researches concerning the true picture of atom and its
elemental particles. However, there are several properties of molecules
or compounds that the classical theories cannot explain. For example,
the concept of spin angular momentum and other intrinsic properties.
Since atom consists of elementary particles whose size and dimension
are very small, then the use of quantum theories along with classical
theories provides a better objective to study molecular structure and
symmetry. This indicates that concepts such as orbital properties,
angular momentum, spin, coupling, bonding and anti-bonding molecular
orbitals and other are subjects of atomic and molecular structure.
COURSE COMPETENCIES
Atomic and molecular symmetry (CHM 307) is a three credits unit

course designed to cover the following concepts: Schrödinger equation.
Helium atom, ground and excited states, spin and Pauli principles,
hydrogen molecule, comparison of molecular orbital and Valence bond
theories; concepts of resonance and configuration of orbital for historic
molecular, Walsh rules. Rotational and vibrational bond length and
angles. Brief mention of other methods, atomic spectra, Russell
Sounder’s coupling, orbital and spin angular momentum. Use of
symmetry in chemistry. Heat capacities of solids. Theory of bonding in
hydrogen molecular ion and hydrogen atom. Rotation and vibration of
molecules. Heat capacities of crystals. This textbook arranged the topics
into six different groups, identified as studied section.
This course is aimed to bring the student to the knowledge of

fundamental aspects of atomic and molecular symmetry including
derivation of Schrodinger equation, application of Schrodinger equation
to orbitals, solving orbitals problems, particle in a one-dimensional box,
etc. Molecular spectroscopy theories are also considered including,
vibrational, rotational, electronic and rovibrational spectroscopies. The
concept of coupling, resonance and Wlsh’s rule are also considered.
Considerations and discussions are also presented for symmetry and
group theory, with special references to symmetry element, symmetry
point group, classification of point group and application of symmetry.
iv
The book is concluded by discussion of heat capacity of crystal solid.

Several laws associated with heat capacity are derived and explained in
study section 6. These included Dulong and Petite law, Francis Lois law
and the Einstein law.
COURSE OBJECTIVES
When you have studied this course, you should be able to:
i. Understand the Schrodinger equation, its derivation from first

principle and application in solving molecular structure problems.
ii. know how to apply the Schrödinger equation to find solution to
some problems including a particle in a one dimensional box,
hydrogen molecular ion problem, hydrogen and helium atoms
problems
iii. understand the concept of spin, angular momentum and coupling
(spin-spin coupling, Russell-Saunders coupling and JJ coupling)
iv. know the concept of molecular spectroscopic with detail
discussion of dipole requirements for spectroscopic transition
(vibrational, rotational, electronic and rovibrational
spectroscopies)
v. explain the Walsh’s rule, Walsh’s diagram and their application
vi. explain the concept of resonance
vii. explore the significant of Dulong and Petite as well as Einstein
laws in calculating the heat capacity of solid crystal
viii. bring the student to the understanding of the meaning of
symmetry, group theory, symmetry elements and their application
to molecular problems.
ix. explain the concept of bonding in molecules using hybridization,
the valence bond and molecular orbital theories
WORKING THROUGH THIS COURSE
The course is structured into five models. Modules 1 to 3 consist of two

units each while modules 4 and 5 consist of one unit each. It is necessary
that for the student to study and understand the content of all the units in
the respective modules.
You will be provided with the following materials:
1. Course Guide
2. Study Units
v
STUDY UNITS
The course is divided into three modules. Each module consist of two
units as shown below
Module 1
Study Unit 1: The Schrödinger equation

Study Unit 2: Theories of bonding
Module 2
Study Unit 1: Molecular Spectroscopy

Study Unit 2: Coupling in Spectroscopy
Module 3
Study Unit 1: Symmetry and Group Theory

Study Unit 2: Heat capacity of solid Crystal
Study unit 1 (in module 1) introduces the Schrodinger equation and

derived the equation from first principle. The components of the
equation (including orbitals, wave function, Hamiltonianm) are
highlighted and discussed. The use of the Schrodinger equation in
solving some quantum chemical and structural problems are also
discussed in study section 1. Symmetric/anti-symmetric wave functions,
Pauli’s exclusion principle are also discussed in study section 1
In study unit 2 (in module 1), theories of bonding are introduced. The
valence bond theory and molecular theory are discussed in derail. The
concept of hybridization, types of hybridization and solving problems
related to hybridization are also discussed in this study section.
Hydrogen molecular ion, hydrogen and helium atoms’ problem are
solved using the Schrodinger equation.
In module 2 study unit 1, molecular spectroscopy is introduced with

special reference to vibrational, rotational, rovibration and electronic
spectroscopy. The use of simple harmonic oscillator and Hooke’s
models in explaining vibrational and rotational spectroscopy have been
deeply treated;
In study unit 2 of module 2, the concept of coupling with special

reference to spin-orbit, Russell-Sanuders and JJ coupling,
vi
In study unit 1 of module 3, symmetry and group theory are discussed

with special reference to symmetry group, group theory, symmetry
elements, symmetry operations and application of symmetry.
Finally, in study unit 2, heat capacity is defined. Models (Dulong and

Petite, Loius and Einstein) explaining heat capacity of solid crystal are
also discussed in detail.
REFERENCES AND FURTHER READNGS
Textbooks referred to in the development of each units are presented at

the end of the units. However, list of some General references are
presented below:
Allinger, N. L (2010). Molecular structure: Understanding steric and

electronic effects from molecular mechanics. John Willey and Son, USA
Aruldhas (2007). Molecular structure and spectroscopy. Prentice Ha;; of
India
Atkins, P. and De Paula, J. (2010). Atkins’Physical chemistry. 9th

Edition. Oxford University Press. UK.
Banwell, C. N. (1983), Fundamental of molecular spectroscopy,

McGraw-Hill International. UK
Demaison, J., Boggs, J. E. and Csaazar, A. G. (2010). Equilibrium

molecular structures. CRC press. Taylor and Francis group, UK
Dhaduk, B. (2019). A textbook of physical Chemistry. Lambert

Publishing, UK
Engel T. and Reid, P. (2005). Physical chemistry. Pearson Cummings.

San Francisco. New York.
Hofmann, A. (2018). Physical Chemistry essentials. Springer

International Publishing. Switzerland
Job, G. and Ruffler R. (2019). Physical chemistry from different angle.

Springer International Publishing. Switzerland.
Lagana, A and Parker, G. A. (2018). Chemical reactions. Springer

Monk, P. (2004). Physical chemistry: Understanding the Chemical

World. John Wiley and Sons Ltd. England.
vii
Struve, W. S. (1989). Fundamental of molecular spectroscopy. John

Willey and Sons. New York
Struvel, W. S. (1987), Fundamental of molecular spectroscopy Springer

Tamvakis, K. (2019). Basic quantum mechanics. Springer International

Publishing. Switzerland AG
Telxeira-Dias, J. J. C. (2017). Molecular physical chemistry. Springer

International Publishing, Switzerland.
PRESENTATION SCHEDULE
This course is presented in three different modules. Each module

consists of two study units. Each module begins with introduction, study
outcomes and main content. Within the main content, fundamental facts
are presented along with inline worked examples and answers. Each unit
ends with summary, conclusion, bibliography, self assessment
questions/answers and activity for student to test their comprehension.
ASSESSMENT
There are two aspects of assessment for this course: the tutor-marked
assignment (TMA) and end of course examination. The TMAs shall
constitute the continuous assessment component of the course. They will
be marked by the tutor and equally account for 30 % of the total course
score. Each learner shall be examined in four TMAs before the end of
course examination. The end of course examination shall constitute 70%
of the total course score.
HOW TO GET THE MOST FROM THE COURSE
Student are expected to comprehends best information out of this course

through careful study of each units. It is recommended that student
should test their ability to answer questions that follow each unit as well
as questions in reference materials related to this course.
viii
CONTENT PAGE
MODULE1…………………………………….. 1
Unit 1: The Schrodinger Equation…………………. 1

Unit 2: Theory of Bonding………………………… 24
MODULE 2……………………………………. 66
Unit 1: Molecular Spectroscopy………………….... 66

Unit 2: Coupling in Spectroscopy………………… 96
MODULE 3……………………………………. 107
Unit 1 Group Theory and Symmetry……………… 107

Unit 2: Heat Capacity of Solid and Crystals……… 119
CHM 307 MODULE 1
MODULE 1
UNIT 1 THE SCHRODINGER EQUATION
1.0 Introduction
2.0 Intended Learning Outcome for Study Section 1
3.0 Main Content
3.1 The time independent Schrödinger equation
3.1.1 The wave function
3.1.2 The Operator
3.1.3 Schrödinger equation and orbital
3.2 Orthogonality
3.3 Solution of the Schrödinger Equation for a One Electron
System
3.4 A Particle in a One-dimension Box
3.5 Symmetric/Antisymmetric Wave Functions
3.6 Pauli’s Exclusion Principles
4.0 (i) Self Assessment Exercise and Answers
(ii) Class Activity
5.0 Conclusion
6.0 Summary
7.0 References/Further Readings
1.0 INTRODUCTION
Atom consists of proton, electron and neutron. The proton is positively

charged and is about 1836 times heavier than the negatively charged
electron. Neutron, which was discovered in 1932 has no charge and is
slightly heavier than the proton. The first set of investigation on the
structure of atom started between 1908 and 1913, when Rutherford,
Hans Geiger and Ernest Marsden repeatedly passed a beam of alpha
particle through a thin metal foil in the Physical Laboratories of the
University of Manchester and observed the deflection of the particle
through a fluorescence screen. In their experiment, they discovered that
most of the alpha particle passed through the foil undeflected, few were
strongly deflected and others were deflected backward. From the
findings of their experiment, they noted that such large deflection is
possible if the positive charge was concentrated in a tiny heavy nucleus
and concluded that every atom contains a nucleus where its positive
charge and most of its mass are concentrated. In 1904, J. J. Thompson
had suggested that the positive charges were spread throughout the atom
but Rutherford and co-workers refuted this fact on the grounds that if it
were so, then once the high energy atom penetrates the atoms, the
repulsive forces would have fallen off and eventually become zero.
Nowadays, it is known that atom contain Z number of proton and
number of Z electrons (where Z is the atomic number). The mass of the
1
CHM 307 ATOMIC AND MOLECULAR STRUCTURE AND SYMMETRY
atom is concentrated in the central nucleus (which contains proton and

neutron, collectively called nucleons). The nucleus is held together by
strong nuclear forces while the nucleus and the electrons are held
together by columbic force of attraction. In 1911, Rutherford proposed
the planetary model of the atom, which stated that electron revolves
around the nucleus. However, this model was exposed to several
criticism. Classically, electromagnetic theory expects an accelerating
ally charge particle to radiate electromagnetic waves. Also, a rotating
charge radiating electromagnetic waves with changing velocity and
direction will gradually lose energy and the atom will be unstable and
eventually collapse.
In 1913, Niels Bohr offered explanation to the Rutherford theory

through the concept of quantization of energy in the hydrogen atom.
Bohr stated the energy of electron in hydrogen is quantized with electron
allowed to move only in a number of allowed circle.
Bohr found that when hydrogen gas is heated, it emits electromagnetic

radiation, characterised by certain distinct frequencies. Such spectral
frequencies were explained according to equation 1.1
= = − 1.1
where nb = 1, 2, 3 ......, na = 2, 3 .. na> nb and R is the Rydberg
constant = 1.096776  105cm-1
Classically, all frequencies of light ought to have been emitted but this is
not true hence Einstein equation implies that the hydrogen atom exist in
certain energy states. Indeed, an atom can has only certain energies, E1,
E2, E3 ............. These allowed states of constant energy are called the
stationary states. An atom in a stationary state can only emit radiation
when its makes transition from a stationary state of higher level to the
stationary states of lower energy and will therefore satisfied equations
2.2 and 2.3;
EHigher - ELower = hv 1.2

Ea - Eb = hv 1.3
Combination of equations 2.1 and 2.3, yields equation 1.4
− = ℎ − 1.4
The implication of equation 8 is that the energies of the H-atom
stationary states can be written as
= − 1.5
2
CHM 307 MODULE 1
The major limitation of the Bohr theory arises from the use of classical
mechanics to describe the motion of an electron in an atom. Evidence
obtained from spectra of atoms reveals discrete frequencies which
indicates that only certain energies of motion is allowed and that the
electronic energy is quantized. Classically, continuous range of energies
are possible but quantum mechanically, the energy is restricted to certain
permissible values.
Although Bohr model was satisfactory in explaining the hydrogen atom,

it fails to explain poly electron systems. In order to extend quantization
to systems with two or more electrons, Louis de Broglie in 1923 found
that just as light shows both wave and particle aspect, matter also has a
dual nature, as well as showing particle like behaviour, electron could
also show wave like behaviour, which manifest itself in the quantized
energy levels of electrons in atoms and molecules. For photons, we
have, Ephoton = hv. Einstein special theory of relativity gives the energy
of a photon as Ephoton = Pc, where P is the momentum of the photon and
c is the speed of light. Equating the two equations, we have hv = pc
and since v = , we have
= or λ = =
1.6
In 1927, the German physicist, Werner Heisenberg stated that the more
precise the position of some particle is determine, the less precisely the
momentum can be known and vice versa. However,, Earle Hesse
Kennard and Hermann Wey in 1928 were able to derived the formal
inequality that relates the standard deviation of position, ax and that of
momentum ap as follows,
ħ
. ≥ 1.7
In quantum mechanics, uncertainty principle is any of the variety

mathematical inequalities that sustain a fundamental limit to the
precision with which certain pairs of complementary physical properties
can be known. Uncertainty principle is inherent in the properties of all
wave like systems and it originate from the de Broglie wave matter
duality principle. In quantum chemistry, the uncertainty principle is
mostly use to explore the relationship between simultaneous
measurement of position and momentum. Therefore, the principle can be
restated as, the product of the uncertainties in position and in momentum
is in the order of magnitude of Planck constant or greater i.e.
ħ
∆ .∆ ≥ 1.8
where ħ is the reduced Planck constant. ħ =
3
2.0` INTENDED LEARNING OUTCOMES (ILOS)
When you have studied this session, you should be able to:
 Comprehends developmental stages of quantum chemistry and

associated models such as Einstein, Bohr, Planck, etc.
 Know how to derive time independent Schrödinger equation from
first principles
 Interpret the various components of the Schrödinger equation
(Wave function, operator, eigen value, etc) and their physical
significant.
 Apply the theory of Schrödinger to the concept of orbital
 Answer questions related to the Schrödinger equation
 Understand the concept of orthogonality
 Understand how to use Schrodinger equation to find solution to a
particle in a one-dimensional box
 Understand the concept of symmetric and anti-symmetry
 Understand Pauli’s exclusion principles
 Be able to solve quantitative and qualitative problems associated
with the Schrodinger equation
3.0 MAIN CONTENT
3.1 The time independent Schrödinger equation
The Schrödinger equation is like the Newton’ s law and the law of
conservation of energy in classical physics because it aids in predicting
the future behaviour of dynamic system. This work of Schrödinger was
initiated by Einstein in 1925, when he published a paper on quantum
theory of ideal gas, and the de Broglie theory of matter waves. However,
in 1926 Erwin Schrödinger proposed an equation that describes the
evolution of a quantum mechanical system è SWE which represents
quantum equations of motion in the following forms:
−ћ  
+ ( )( , ) = ћ
2
−ћ 
+ ( ) ( , ) = ћ
2
This is an equation that describes how the quantum state of a system

changes with time. We can derive, the Schrödinger equation using the
unique equation,
4
CHM 307 MODULE 1
Ψ = 1.9
Differentiating equation 1.10 with respect to x, we have;

= Acos 1.10
Taking a second derivative of equation 13 with respect to x yields

equation 1.11;
= − Asin 1.11
Since ψ = , equation 2.11 can be simplified to the form given by

equation 1.12
= − ψ 1.12
Equation 1.12 can be simplified by applying the de Broglie equation,

which relates particle momentum to wavelength as, λ = . Therefore,
λ = and substituting for λ in equation 1.12, equation 1.13 is
obtained
= ψ= ψ 1.13
.
The total energy of a system is the sum of the kinetic energy (KE = ½
mv2) and the potential energy (U), i. e. E = KE + U = ½ mv2 + U and
v2 = 2/m (E – U). Modification of equation 2.13 through substituting the
value of v2 by 2/m (E – U) leads to equation 2.14
= (E − U)ψ 1.14
Introducing the reduced Planck constant, ħ = h/2π, equation 2.14
becomes,
= (E − U)ψ
ħ
1.15
Equations 2.14 and 2.15 are the various differential forms of the time
independent Schrödinger equation for a one-dimensional system. For a
three-dimensional system, the following equations are obtained,
+ + = ( − )
1.16
=( + + )ψ = ( − )ψ
1.17
= ∇2 ψ = ( − )ψ 1.18
5
= ∇2 ψ = ( − )ψ 1.19
ħ
where ∇2 is called Laplacian operator, ∇= + + . . The
Schrödinger equation can be re-arranged by collecting like terms as
follows,
ћ
+ ψ = ψ or + ψ= ψ
1.20
The first term + is called the Hamiltonian operator, Ĥ

which operates on ψ to give the energy E and the wave function.
Therefore, the general form of the Schrödinger equation can be written
as ĤΨ = Eψ. The Schrödinger equation is on eigen equation or eigen
function of the form (operator) (function) = (numerical value) x
(function). The numerical function in this case is the energy and is
called an eigen value. Solving the Schrödinger equation involves
finding the value of the eigen value. The importance of eigen value
equation is that it is consistent with the following patterns,
(Energy operator) (wave function) = (Energy) (wave function)
(operator) (wave function) = (observable) (wave function)
From the above, if we know both ψ and the operator corresponding to
the observable of interest, we can predict the outcome of an observation
of that property.
3.1.1 The wave functions
The Schrödinger equation is the fundamental equation in quantum

mechanics. The wave function does not have any physical significant
but the square of the wave function represents the probability density of
finding a system in a given time. This assertion was proposed by Max
Born. Max, also proposed four conditions that must be fulfilled when
the solution to the Schrödinger equation is sought for. Born’s conditions
to be imposed on the wave function, ψ are:
i. The wave function must be single valued. This means that for any
given values of x and t ψ, must have a unique value. This is a
way of guaranteeing that there is only a single value for the
probability of the system being in a given state. Actually, if ψ is
a proper mathematical function, it will satisfy this requirement
automatically, since one condition all functions must satisfy is
that they are single-valued.
ii. The wave function must be quadratically integratable. This
implies that, the integral of |ψ| over all space must be finite.
This is another way of saying that it must be possible to use
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CHM 307 MODULE 1
|ψ| as a probability density, since any probability density must

integrate over all space to give a value of 1, which is clearly not
possible if the integral of |ψ| is infinite. One consequence of this
proposal is that the wave function must tend to 0 for infinite
distances.
iii. The wave function must be continuous at all points, indicating
that there should not be a sudden jump in the probability density
when moving through space. If a function has a discontinuity
such as a sharp step upwards or downwards, this can be seen as a
limiting case of a very rapid change in the function. Such a rapid
change would mean that the derivative of the function was very
large (either a very large positive or negative number). In the
limit of a step function, this would imply an infinite derivative.
Since the momentum of the system is found using the momentum
operator, which is a first order derivative, this would imply an
infinite momentum, which is not possible in a physically realistic
system.
iv. All first-order derivatives of the wave function must be
continuous. Following the same reasoning as in condition iii, a
discontinuous first derivative would imply an infinite second
derivative, and since the energy of the system is found using the
second derivative, a discontinuous first derivative would imply an
infinite energy, which is not physically realistic.
3.1.2 The Operator
An operator is an instruction, a symbol which tells us to perform one or

more mathematical acts on a function, say f(x). The essential point is
that they act on a function. Operators act on everything to the right,
unless the action is constrained by brackets.
i. Addition and subtraction rule for operators:

Â ±Â ( )= Â ( )±Â ( )
1.21
ii. The product of two operators requires successive operation. For
example,
Â . Â ( ) = Â Â . ( )) 1.22
It should be noted that the product of two operators is the third operator,
i.e, Â = Â . Â
iii. Two operators are said to commute if the obey the simple
operator expression
Â . Â = Â . Â − Â . Â = 0 . This indicate that Â . Â =
Â .Â
7
The commutivity of two operators implies that the observables

associated with these two operators can be measured simultaneously.
This is contrary to the Heisenberg uncertainty principles which requires
non commutivity. For example, the non-commutivity of the position and
the momentum operators (the inability to simultaneously determine
particles position and its momentum) is represented with the Heisenberg
ħ
uncertainty principle as ∆ . ∆ ≥ = |〈[ , ̂ ]〉|.
3.1.3 Schrödinger equation and orbital
The solution of the Schrödinger equation involves finding the eigen

value through the eigen function. Several wave functions such as 1, 2,
3, 4,….. may satisfy the requirements for the Schrödinger equation
and each of them has corresponding eigen value such as the energy, E1,
E2, E3, E4……. respectively. Each of this wave function is called an
orbital and the square of each of them represent the probability of
finding electron within a given volume element. For example, 1 can be
used to represent the ground state orbital of hydrogen atom because its
single electron will first occupy the first orbital. The energy of this
orbital will be E1.
Each atom has a number of acceptable solutions to the Schrödinger

wave equation and each orbital may be described by a set of three
quantum numbers namely,
i. The Principal quantum number, n: describes the energy level of

electron
ii. The subsidiary quantum number, l: describes the shape of orbital
occupied by electrons. Values of l includes the integers and zero,
i.e 0, 1, 2, 3, 4…. When l = 0, 1, 2 and 3, the orbitals are s-
orbital, the p-orbital, the d-orbital and the f-orbital respectively.
The letter s, p, d and f originate from spectroscopy and are sharp,
principal, diffuse and fundamental respectively
iii. The magnetic quantum number, m: describes the paramagnetic or
diamagnetic properties of electron. When l = 0, m = 0
Based on allowed solutions to the Schrödinger equation, orbitals can

generally be classified into three groups. These are
i. Those whose probability of finding electrons is a function of

distance, r from the nucleus and the probability, |ψ| is the same
in all direction. The s-orbital is the only orbital in this group
ii. Those whose wave function depends on the distant from the
nucleus and on the direction in space (x, y, z). Orbitals in this
group are characterised by subsidiary quantum number equal
8
CHM 307 MODULE 1
to 1 and are called p-orbital. There are three possible values of

the magnetic quantum number, i.e m = -1, 0, +1, indicating
that there are three sub orbitals for orbital in this group. These
are,
 x = f(r). f(x)
 y = f(r). f(y)
 z = f(r). f(z)
These sub orbitals have the same energy. Therefore, there are three
degenerate orbitals for each of the value of n = 2, 3, 4
iii. The third group consist of orbitals whose wave function
depends on distance from the nucleus, r and also on two
directions in space. For example, the d and f orbitals. For the
d-orbital, the subsidiary quantum number, is 2 and the
magnetic quantum number, m = 4, i.e., -2, -1, 0, +1, +2.
Therefore, there are four degenerate sub orbitals for the d-
orbital formed when n = 3, 4, 5. These are,
i. x-y = f(r). f(x). f(y)
ii. x-z = f(r). f(x). f(z)
iii. y-z = f(r). f(y). f(z)
iv.  = f(r). f(z). f(z)
v.  = f(r). f(z2). f(y2)
The subsidiary quantum number for the f-orbital, l is 3 indicating that

the magnetic quantum number m = 7, i.e. -3, -2, -1, 0, +1, +2, +3.
Therefore, there are seven degenerates sub orbitals for the f- orbital,
which are formed when n = 4, 5, 6.
3.2 Orthogonality
If the wave function has different quantum numbers, then their overlap
is zero and for two wave function, the overlap can be written as,
  =
where is called the Kronecker delta. It has the property such that
= 0,if m = n and = 1, if m n.
3.3 Solution of the Schrödinger equation for a one electron

system
Hydrogen atom, He+ and Li2+ are example of a one electron system. The
Schrödinger equation can be solved for these systems by converting the
Cartesian coordinates (x, y, z) to the polar coordinates (p, , and  ). The
coordinate of a point, P measured from the origin are x, y and z in
9
Cartesian coordinate and p,  and  respectively (See Fig 1.1). The

relationship between Cartesian and polar coordinates are,
i. z = pros
ii. y = spincos
iii. z = spincos
The three-dimension Schrödinger equation can be written as, ∇2 ψ +

( − )ψ = 0 . where ∇ is the Laplacian operator, as defined
before. Changing to polar coordinates, ∇2 ψ becomes,
. + . + . 
    
1.23
Without proof, the solution to equation 1.23 is in the form given by

equation 1.24
iv. ψ = R( ). (). ()
1.24
Fig. 1.1: Relationship between polar and Cartesian coordinates
Equation 1.24 can be spitted into three components as follows,
i R(p) is a function of the distance from the nucleus and depends

on the quantum number, n and l.
ii. () is a function that depends on the quantum number, l and m
iii. () is a function which depends only on m.
From the above information, we can re-write equation 28 as
follows,
ψ = R( ) , + P ,
1.25
10
CHM 307 MODULE 1
where R( ) , is the radial wave function which depends on the

quantum number, n and l while P , is the total angular wave function
which depend on the quantum number m and l. Although the radial
function has no physical significant, the square of it, defines the
probability of finding electron on a small volume element, dv. It has
been found that for a given value of p, the number of small volumes is
4πp2. Therefore, the probability of an electron being at a distance p from
the nucleus is 4πp2.R2. This quantity is called the radial distribution
function. Fig. 1.2 shows plots of radial distribution functions for various
orbital. From the plots, it is evident that the probability is zero at the
nucleus (i.e. p = 0) and for 1s, 2s and 3s, the most probable distance
increases as the principal quantum number increases. If we compare the
plots for 2s with that of 2p or 3s with that of 3p, it is evident that the
most probable distance decreases with increase in the subsidiary
quantum number.
Fig. 1.2: Radial distribution functions for various orbitals
3.4 Symmetric/Antisymmetric Wave Functions
For a system of identical particles, which are indistinguishable from

each other, interchanging the particles occupying any pair of states will
not change the probability density,|ψ| of the system. Let the particle
wave function beψ , and ψ , ). The probability density of the two
particles wave function will agree with the following expression
ψ( , = ψ( , )
)
1.26
Equation 45 can be fulfilled under two major conditions. These are,
(i) symmetric case:ψ( , ) = ψ( , )
1.27
11
(ii) Antisymmetric case:ψ( , ) = −ψ( , )

1.28
From the above, it can be deduced that particles whose wave function
are symmetric under particle interchange have integral or zero intrinsic
spin (i,e, 0, 1, 2,3...) and are termed bosons. On the other hand, particles
whose wave functions are anti-symmetric under particle interchange
have half-integral intrinsic spin . , , , , and are termed
Fermions. Electrons are Fermions. Any number of bosons may occupy

the same state but not two Fermions may occupy the same state.
Worked Example 1
Given a wave fonction,  = sinnx, find the solution to the Schrödinger

équation,
Solution
The wave function Is defined as,  = sinnx. Operating  with Ĥ, we

have,
−ћ
Ĥ = . ( )
2
ћ
= . ( )
2
ℎ
Ĥ = . (note that  = sinnx)
2
Worked Example 2
Show that  = e are also an eigen function of Ĥ =

− . .Hence calculate the energy of the system if a = 2
Solution
Since  = e ,

= − e

= e
Operating the given wave on the Hamiltonian operator, we have,
ћ
Ĥ = − . (e )
2
12
CHM 307 MODULE 1
ћ
Ĥ = − ( e )
2
ћ
Ĥ = − 
2
The general form of the Schrödinger equation is Ĥ = E. Therefore,
comparing this to the above expression, the energy of the system is E =
− . Therefore, when a =2, the energy, E=-
Worked example 3
Normalize the following wave function,  = Asinnx, given that x lies

in the range 0 to π
Solution
The basic condition for a wave to be normalize is that, ∫ ψψ∗ δ = 1.

Since ψψ∗ = ψ , then it can be stated that the given wave,  =
Asinnx, is normalize under the following condition,
ψψ∗ dx = 1
( ) = 1
. = 1
The solution of the integral, ∫ . is . Therefore, for the

normalization condition to be fulfilled, . must be equal to unity.
That is . = 1, which gives = . Hence the normalized wave
function is ( ). = is called normalization factor.
Worked example 4
Under what conditions can you say that a wave function is orthogonal?
Hence derive the orthogonal relationship for a particle in a one-
dimension box.
Solution
If the wave function has different quantum numbers, then their overlap
is zero and for two wave function, the overlap can be written as,
  =
13
where is called the Kronecker delta. It has the property such that
= 0,if m = n and = 1, if m n. let us write the orthogonality
relationship for a particle in a one-dimensional box for example. The
wave function for this particle is  = . If the there
exist different quantum numbers, m and n, then, ∫   =
and for the particle, we have,
2
3.5 Pauli’s Exclusion Principle
The fundamental idea behind the Pauli’s exclusion principle is that no

two electrons in an atom can have the same four quantum numbers (n, l,
m and ms). The theory considers symmetry and anti-symmetry
properties of a complete wave function (which include spatial and spin
coordinates) with respect to interchange of spatial and spin coordinates
of any two particles.
Let us consider the wave function with respect to  and  electrons in

helium, which can be written as,
 = 1 (1)1s(2)
1.27
Since electron is indistinguishable, the complete wave function can be

written according to equation 1.28, which re-arrange to equation 1.29,
 = 1 (1)1s(2) + 1 (2)1s(1)
1.28
 = 1 (1)1s(2)[(1)(2) + (2)(1)]
1.29
The requirements of equations 1.28 and 1.29 can also be met by the
underlisted equations (equations 1.30 and 1.31)
 = 1 (1)1s(2) − 1 (2)1s(1)
1.30
 = 1 (1)1s(2)[((1)(2) − (2)(1)]
1.31
A close examination of equations 1.30 to 1.31 reveals that the wave

function can be separated into spatial part [1 (1)1s(2)] and the spin
14
CHM 307 MODULE 1
part ([((1)(2) − (2)(1)]) or [((1)(2) + (2)(1)]. The

product of the orbital with the spin function is called spin orbital,
Equation 1.29 is symmetry to electron interchange while equation 1.31
is anti-symmetry to electron interchange.
Pauli Exclusion Principle can be effectively analysed by considering a

non-interacting qualifier for a two-particle wave function, which can be
written as a product of two single particle wave function according to
equations 1.32 and 1.33,
ψ , = ψ ( )ψ ( ) 1.32
ψ , = ψ ( )ψ ( )
1.33
where a and b are two different single particle states. Since the particles
are indistinguishable, the system can be considered as a combination of
the two function, ψ ψ . Consequently, the only two correct
normalized combinations that can be obtained are
(i) Symmetric case:

ψ r, = [(ψ (r )ψ ( ) + ψ ( )ψ ( )] 1.34
√
(ii) Anti-symmetric case:
ψ r, = [(ψ (r )ψ ( ) − ψ ( )ψ ( )]
√
1.35
In the case of fermions, if a = b, the ψ = o implying that no two

Fermions can occupy the same state. This is the concept of Pauli
exclusion principle and it is obeyed by Fermions and not by bosons.
However, while fermions obey Femi-Dirac theory, bosons obey Bose-
Einstein theory. Bosons systems therefore display outstanding
properties, such as super-conductivity. Pauli exclusion principle can be
re-stated as follows, the complete wave function for a system of
identical fermions must be anti-symmetry with respect to interchange of
all coordinate of any two particles. For a system of identical bosons, the
complete wave function must be symmetry with respect to interchange
of all coordinate of any two particle.
3.6 A Particle in a one-dimension Box
A particle in a 1-dimensional box is a fundamental quantum mechanical

approximation describing the translational motion of a single particle
confined inside an infinitely deep well without provision for it to escape.
It is an application of a quantum mechanical model to a simplified
system consisting of a particle moving horizontally within an infinitely
deep well from which it cannot escape. The solutions to the problem of a
15
particle in a one-dimensional box involves finding the possible values of

the allowed energy, E and the wave function, ψ(x), whose square gives
us the probability of locating the particle at a certain position within the
box at a given energy level.
To solve the problem for a particle in a 1-dimensional box, the following

steps are required,
i. Defining the potential energy, V, within and outside the box

ii. Solving the one-dimensional Schrödinger equation
iii. Defining the wavefunction
iv. Defining the allowed energies
Consider a particle in in a one-dimension box shown in Fig. 1.3. Three

regions exist These are I, II and III. The particle can only move in
region II and not I and III. This is a simple problem that is similar to an
electron in atom considered to move within a distant x, which is between
x = o and x = a. The potential energy is 0 inside the box (V=0 for
0<x<L) and goes to infinity at the walls of the box (V=∞ for x<0 or
x>L). It is assumed the walls have infinite potential energy to account
for the fact that the particle has zero probability of being at the walls or
outside the box.
The appropriate wave function for this system will be related to the
Schrödinger equation for a one dimension according to equation
+ ( − )ψ = 0 1.36
ћ
Since the potential energy V, is zero inside the box (i.e. location II)
equation 1.36 becomes rearrange to 1.37 by putting V = 0:
+ ψ 1.37
ћ
Fig.1.3: A particle in a one-dimension box
16
CHM 307 MODULE 1
Solution of equation 1.37 is
ψ (x) = sin + cos

ћ ћ
1.38
Since the potential outside the box is zero, the probability of finding the
particle must have a value of zero at these points. In order to satisfy the
boundary conditions at x = 0, we have, ψ(0) = sin(0) + os (0) =
Therefore, B = 0 and the second boundary condition implies that x = a.
Hence,
ψ (a ) = sin =0 1.39
ћ
The above equation is only true if = .where n is an

ћ
integral (n = 1,2, 3,). ћ is the reduced Planck constant. ћ = h/2 .
Substituting for into equation 1.38, we have,

ћ
 = 1.40
In order to calculate the value of A, it is assumed that the total

probability of finding the particle inside the box is unity (1) indicating
that there is no probability of the particle to be outside the box. This
correspond to the wave function been normalized, i.e., ∫  = 1.
Normalizing equation 1.40, equation 1.41 is obtained
∫ = 1
1.41
From integral table, the solution to the above equation gives =
and the normalised wave function is expressed in equation 1.42
, = 1.43
Since = , it follows that = . Substituting for

ћ ћ
ћ = = , we have equation 1.44, which simplified to equation

1.45 (that gives the expression for the allowed energy of a particle in a
one dimension box
( ) ( )
=
1.44
= 1.45
17
where n = 1, 2, 3, 4 ………., From equation 69, a particle moving

between two points in a line can have only the energies given by =
. Such discrete energy levels are characteristic of solution of the
Schrödinger equation for bound particles. No such energy level is
expected on the basis of classical mechanics for example when n = 1,
= indicating that a particle must have at least an energy value
equal to h /8ma2. It is only this value of E that makes the wave function,
2
a well behave as a continuous function. The state of lowest energy for a

quantum system is termed its ground state. The residual energy of the
ground state, that is, the energy in excess of the classical minimum, is
known as zero-point energy. In effect, the kinetic energy, hence the
momentum, of a bound particle cannot be reduced to zero. Confining the
particle to be between 0 and ‘a’ implies that the wave function must be 0
at x = 0 and x= a. This also means that the energy is quantized. This can
be compared to the vibration of a string fix at both ends. A zero- point
energy is defined whenever a particle is constrained to a finite region
otherwise, the uncertainty principle would have been violated. The
minimum value of momentum is found by equating E1 to p2/2m, giving
Pmin = ±h/2a. This can be expressed as an uncertainty in momentum
given by ∆p ≈ h/a. Coupling this with the uncertainty in position, ∆x ≈ a,
from the size of the box, we can write ∆x∆p ≈ h, which agrees with the
Heisenberg uncertainty principle
On the other hand, when n = 2, 3, 4, 5, we have

4ℎ
= =2
8
9ℎ
= =3
8
16ℎ
= =4
8
From the above, it can be seen that the energy is restricted to a certain
permissible value. For example, energies are multiple of 4, 9, 16 for n =
2, 3 and 4 respectively, hence the energy is quantised. The particle,
therefore, always has a positive energy. This contrasts with classical
systems, where the particle can have zero energy by resting
motionlessly. This can be explained in terms of the uncertainty
principle, which states that the product of the uncertainties in the
position and momentum of a particle is limited by ∆x∆P ≥ћ/2.It can be
shown that the uncertainty in the position of the particle is proportional
to the width of the box and that the uncertainty in momentum is roughly
inversely proportional to the width of the box. The kinetic energy of a
particle in a one dimension box is given as KE = p2/(2m) and hence the
minimum kinetic energy of the particle in a box is inversely proportional
18
CHM 307 MODULE 1
to the mass and the square of the well width.The wavefunction for a
particle in a box at the n=1 and n=2 energy levels is shown in Fig. 1.4
Fig. 1.4: Diagram showing the wave function for n = 1 and n = 2
The probability of finding a particle a certain spot in the box is

determined by squaring the wave function. The probability distribution
for a particle in a box at the n=1 and n=2 energy levels takes the pattern
shown in Fig. 1.4. It can be seen from Fig. 1.5 that the number of nodes
(places where the particle has zero probability of being located)
increases with increasing energy n. Also, as the energy of the particle
becomes greater, the quantum mechanical model breaks down as the
energy levels get closer together and overlap, forming a
continuum. This continuum means the particle is free and can have any
energy value. At such high energies, the classical mechanical model is
applied as the particle behaves more like a continuous wave. Therefore,
the particle in a box problem is an example of wave particle duality.
Fig. 1.5: Diagram showing the variation of probability function for
n= 1 and n = 2 levels
4.0 (i) Self-Assessments Exercise and Answers
1. What is the major limitation of Bohr’s model?
19
2. Calculate the wave length of electron moving at 2 x 106m/s using

the de Broglie equation
3. Construct the Hamiltonian operator for a system whose energy is
given as = + + + ( , ,)
4. if there are two particles in the system such that their masses are
m1 and m2, construct the Hamiltonian for the system.
5. What is spin orbital?
Answers to Self-Assessment Exercises
1. The major limitation of the Bohr theory arises from the use of
classical mechanics to describe the motion of an electron in an
atom. Evidence obtained from spectra of atoms reveals discrete
frequencies which indicates that only certain energies of motion
is allowed and that the electronic energy is quantized. Classically,
continuous range of energies are possible but quantum
mechanically, the energy is restricted to certain permissible
values.
2. The Broglie equation gives the wave length of electromagnetic
radiation, of which electron behaves in similar manner as ,
λ= where m is the mass of electron. m = 9.1 x 10-3 kg.
Therefore,
.
λ= = 3.6 x 10-10m =
( . )
3.6Ao
The result is in the order expected for elementary particles indicating

that unique effect is important in electronic motions.
3. We start by changing the classical momentum component to

quantum mechanical operator, this
− ћd
→Ṕ =
− ћd
→ Ṕ =
ћ
→Ṕ = , Therefore;
− ћd − ћd −ћ
→Ṕ = , =
→Ṕ = , =
20
CHM 307 MODULE 1
→Ṕ = , =
Therefore, the Hamiltonian operator can be written as;

−1 ћ ћ ћ
Ĥ= + + + ( , , )
2
−ћ
= + + + ( , , )
2
−ћ
∇ + = ( , , )
2
Where ∇ is the Laplacian operator, ∇= + +
4. if there are two particles of masses, m1 and m2 and co-ordinate

(x1, y1, z1), (,x2, y2, z2), then the classical energy can be written as:
1 1
= + + + + +
2 2
+ ( , , , , , )
ћ ∇ ћ ∇
And the corresponding Hamiltonian is;Ĥ = − +
( , , , , , )
ћ
= ∇ + ∇ + ( , , , , , )
5. The product of the orbital with the spin function is called spin
orbital
4.0 CONCLUSION
The fundamental wave equation is the Schrodinger equation and its

importance is based on the fact that solutions to quantum systems can be
derived through the Schrodinger equation. To a good extent, the
Schrodinger equation has been used to explain several quantum system
with good degree of certainty especially with the use of some computer
softwares.
5.0 SUMMARY
The energy of a particle is quantized. This means it can only take on

discreet energy values. The lowest possible energy for a particle is not
zero (even at 0 K). This means the particle always has some kinetic
energy. The square of the wavefunction is related to the probability of
finding the particle in a specific position for a given energy level. The
probability changes with increasing energy of the particle and depends
on the position in the box we are attempting to define the energy. In
21
classical physics, the probability of finding the particle is independent of

the energy and the same at all points in the box
6.0 TUTOR MARKED ASSIGNMENT
(1) What are the major properties of a wave system:? (3 minutes)

(2) What are the limitation of the Schrodinger equation in
describing quantum systems (3 minutes)
(3) Differentiate between time dependent and tine independent
wave functions (5 minutes)
7.0 REFERENCES/FURTHER READINGS

Aruldhas (2007). Molecular structure and spectroscopy. Prentice Ha;; of
India




Publishing, UK





22
CHM 307 MODULE 1

Struvel, W. S. (1987), Fundamental of molecular spectroscopy Springer



23
UNIT 2 THEORY OF BONDING
CONTENT
1.0 Introduction
2.0 Intended Learning Outcome
3.0 Main Content
3.1 The valence bond theory
3.2 Hybridization theory
3.2.1 Types of hybridization
3.3 Theory of resonance
3.4 Walsh’s rule
3.5 Molecular orbital theory (MOT)
3.5.1 Linear combination of atomic orbital (LCAO)
3.6 Bond order
3.6.1 Bond order for heteronuclear diatomic molecule
3.7 Theory of bonding in some systems
3.8 Theory of bonding in hydrogen molecular ion
3.9 Theory of bonding in hydrogen atom
3.10 Theory of bonding in helium atom
4.0 (i) Self-Assessment Questions and Answers
(ii) Class Activity
5.0 Conclusion
6.0 Summary
1.0 INTRODUCTION
There are two major approaches that can be used to calculate molecular
structure. These are the valence bond theory (VBT) and the molecular
orbital theory (MOT). VBT assumes that all bonds are localized bonds
formed between two atoms by the donation of an electron from each
atom and that electrons occupy atomic orbitals of individual atoms
within a molecule, and that the electrons of one atom are attracted to the
nucleus of another atom. The basis of VB theory is the Lewis concept of
the electron pair bond. On the other hand, the MOT relies on the
combination of atomic orbitals to form bonding and antibonding
molecular orbitals. The former stabilizes the molecule while the latter
destabilizes the molecule. However, these theories lack the capacity to
explain the nature of bonding in some molecules, hence where the VBT
fails, hybridization theory explain bonding in terms of promotion of
electrons, the formation of hybrid orbitals before overlapping. Beyond
the VBT, the MOT and hybridization, is the quantum mechanics, which
has the potential of explaining chemical bonding in most compounds
24
CHM 307 MODULE 1
by considering the behaviour of electrons during bonding. Combination

of all these theories are discussed in this study section
25
2.0 INTENDED LEARNING OUTCOME
When you have studied this session, you should be able to:
 Understand the valence bond theory of bonding in molecules

and the conditions for overlap
 How atomic orbitals are mixed through hybridization in order
to form bonding
 Know different types of hybridization and provide examples
for each
 Know why resonance hybrid is needed to describe the
chemical structure of some compounds and how to calculate
resonance energy
 Understand the theory and application of Walsh’s rule
 Understand the molecular orbital theory and their applications
in explaining bonding in some compounds
 Differentiate between bonding molecular orbital and
antibonding molecular orbitals
 Understand how pi and sigma bonds are formed
 Use the molecular orbital theory to calculate bond order and
interpret magnetic property, stability and other properties of
some compounds using bond order
 Understand theories of bonding in hydrogen molecular ion,
helium and hydrogen atoms
 Be able to solve mathematical problems associated with
theories of bonding
3.0 MAIN CONTENT
3.1 The Valence bond theory
The VBT considered that a bond is formed when an electron in an

atomic orbital of one atom pairs its spin with that of an electron in
atomic orbital of another atom. For example, in molecular hydrogen, the
spatial wave functions for electron in each of the atom can be written as,
 = ( ) ( )
= ( )(1)( )(2)
105
where A and B denotes the two atomic nuclei. In the case of hydrogen
atom, the outcome of ( )(1) and ( )(2) are equally likely because
the atoms are indistinguishable. The application of quantum mechanics
requires that the total probability should be derived from superposition
26
CHM 307 MODULE 1
of the wave function for each. Hence the valence bond wave function for
hydrogen molecule can be written as,  = ( )(1)( )(2) +
( )(1)( )(2).
The linear combination given by equation 106 will have an energy lower
than that of any of the combining wave function because of constructive
interference between ( )(1)( )(2) and ( )(1)( )(2). This
implies that there will be an enhancement of the probability density of
electron in the intermolecular region.
The valence bond theory relies on the overlap of orbitals of the

combining atoms. Orbital overlap requires that the following conditions
are met,
i. Completely filled orbital cannot overlap. Consequently, only half

filled orbital from one atom can combine with half-filled orbital
from the other atom to form a new orbital, having opposite spin
of electron
ii. The atoms with bonding orbitals should be closely and properly
align with the axis of their orbital
The strength of bond formed depends on the magnitude of the overlap,

the greater the overlap, the greater the bond strength. Overlap orbital has
energy lower than that of the isolated atoms, hence overlapping
stabilises the compound. The stabilization energy (or bond energy) is the
amount of energy given off or released per mole at the time of
overlapping of atomic orbitals to form a bond. Since overlapping
stabilizes the b orbital, it implies that it is a function of the distance of
separation between the combining atoms. There are three major types of
interaction that can be encounter when atoms come close to each other.
These include,
i. Repulsion between nuclei

ii. Repulsion between electrons
iii. Attraction between electron and nuclei.
The strength of overlap increases as the atoms approaches each other

more closely. However, there exist a distance of closest approach such
that forces of repulsion and attraction are in equilibrium. This distance is
called bond length. The closer the atoms are to each other, the greater
the overlap and hence the better is the strength of the bond.
Consequently, molecules with shorter bond length are stronger than
those with longer bond length.
The formation of hydrogen molecule can be explained using the valence

bond theory. In this case, electron from the 1s orbitals of the two
27
hydrogen atoms overlap and form a relatively larger electron cloud

called molecular orbital as shown below
The newly form molecular orbital has energy lower than either of the
two hydrogen atoms, it was formed from. Further explanation of the
dependent of the strength of covalent bond in hydrogen on distance of
separation can be viewed in the potential energy surface shown in Fig.
2.1.
Fig. 2.1: Potential energy diagram of hydrogen molecule
In the diagram, at position A, the two hydrogen atoms are far from each
other but as the atoms comes much closer, the energy drops until it gets
to the minimum at B. After B, further decrease in distance destabilizes
the molecule and leads to increase in repulsion (i.e. the energy
increases). The minimum distance corresponds to the equilibrium bond
length. It is at this point that maximum overlap occurs. The energy
corresponding to the minimum of the curve is called dissociation energy.
It is the maximum energy that stabilizes the molecule. Beyond the
dissociation energy, the molecule will be destabilised.
Overlap in covalent bonded compounds can be due to sigma or pi bond

depending on the molecular orbital and the orientation of the molecule
before overlapping. Sigma bond can be from through one of the
following overlaps
28
CHM 307 MODULE 1
i. s-s overlapping results from the combination of s orbital with one

another. Example is the formation of hydrogen molecule
ii. s-p overlapping occurs when an s-orbital from one atom overlap
with a half-filled p-orbital from another atom. An example of
molecule with s-p overlapping is in the formation of HCl and HF
iii. p-p overlapping can lead to sigma bond when one p-orbital from
one atom overlaps with p-orbital from another orbital at the
internuclear axis. Example is in the formation Cl2, F2, etc. (see
diagram below)
On the other hand, pi bond results from half-filled p-orbitals. The

overlap occurs through lateral or sideward interaction (see diagram
below). S orbital cannot form pi-bond no matter the manner they
combine
Generally, a sigma bond is stronger than a pi bond because the extent of

overlap is greater during the formation of a sigma bond compared to the
formation of a pi bond.
Worked example 1
(a) Why is a sigma bond stronger than a pi bond?

(b) State two conditions that are required before two orbitals can
overlap
(c) What is the different combination of orbitals that can lead to the
formation of overlap in sigma and pi bond. Give at least one
example for each.
29
Solution
(a) A sigma bond is stronger than a pi bond because the extent of

overlap is greater during the formation of a sigma bond compared
to the formation of a pi bond.
(b)
(i) There must be half filled orbital from one atom to combine with
half-filled orbital from the other atom to form a new orbital,
having opposite spin of electron
(ii) The atoms with bonding orbitals should be closely and properly
align with the axis of their orbital
(c) The various types of orbital overlaps for the formation of a sigma
bond are,
i. s-s overlapping results from the combination of s orbital with

one another. Example is the formation of hydrogen molecule
ii. s-p overlapping occurs when an s-orbital from one atom
overlap with a half-filled p-orbital from another atom. E.g. is
in the formation of HCl and HF
iii. p-p overlapping can lead to sigma bond when one p-orbital
from one atom overlaps with p-orbital from another orbital at
the internuclear axis. Example is in the formation Cl2, F2, etc
Pi overlap is formed by lateral or sideward interaction of partially
filled p-orbital of one atom with p-orbital of another atom.
3.2 Hybridization theory
The valence bond theory (VBT) and the molecular orbital theory (MOT)
cannot explain the formation of bonds in some atom or molecules such
as carbon, helium etc. However, the concept of hybridization has been
found to offer useful explanation for most cases that cannot be better
explained by the VBT and MOT models. Hybridization combines
atomic orbitals having comparable energies to form hybrid orbitals equal
in number to the atomic orbitals from which they were formed. Some
conditions required for hybridization to be feasible include the
following,
(i) Only orbital of one single atom will undergoes hybridization.

(ii) The energy levels of the orbitals to be mixed must, be
comparable
(iii) Number of hybrid orbitals generated is equal to the number of
hybridizing orbitals.
(iv) The hybrid orbitals assume the direction of the dominating
orbitals. For example, in sp hybridization, the s-orbital
30
CHM 307 MODULE 1
does not contribute towards the direction but it is the p orbitals

that determine the directional character of the hybrid orbitals.
(v) Hybridization involves the orbitals and not the electrons.
(vi) The electron waves in hybrid orbitals repel each other and thus
tend to be farthest apart.
3.2.1 Types of hybridization
3.2.1.1 Sp hybridization:
Sp hybridization involves the mixing of s and p orbitals to produce two

hybrid orbitals in which the s-character and p-character are equal (i.e. 50
% each). This type of hybridization is sometimes called linear
hybridization and the angle of separation is 180. Diagrammatic
representation of sp hybridization is shown below
sp orbital has two lobes (a character of p orbital) one of which is farther

than the corresponding s or p orbitals and also protrudes farther along
the axis. It is this bigger lobe that involves itself in the process of an
overlap with orbitals of other atoms to form bonds.
Worked example 2
Explain the theory of sp hybridization in BeF2
Solution
Example of sp hybrid orbitals is in the formation of BeF2. The ground

state electronic configuration of Be is 1s22s22p0. . However, when the
atom is excited, one electron in the 2s valence orbital is promoted to the
2p orbital. The S and P orbital then mix and produced sp hybridized
orbital which is capable of overlapping with p-orbital in fluorine to form
BeF2. As shown in the diagram below, the Be atom is at right angle to
the fluorine atoms. Consequently, compounds that witness sp
hybridization are linear compounds.
31
3.2.1.2 SP2 hybridization
Sp2 hybridization involves the mixing of one s-orbital with two p-

orbitals resulting in the formation of three orbitals with 33 and 67 % s
and p characters respectively. The hybrid orbitals lie on a plane father
away from each other and at an angle of 120  as shown below. Example
of compound formation that involves sp3 hybridization is BeF3. The
ground state electronic configuration of Be is 1 2 2 2 2 . From
the electronic configuration, Be is expected to form only one bond since
there is only one bonding electron but the existent of compound such as
BF3, BH3, BCl3 contradict this principle. However, the formation of
such bond is achieved through hybridization.
Scheme for sp2 hybridization
When Be is excited, the one of the 2s electron is promoted to the 2Py

level and the configuration becomes 1 2 2 2 2 . One s-orbital
will then mix with 2p orbitals (Px and py) to form three hybrid orbitals
by a process called sp2 hybridization. The three sp2 hybrid orbitals lies in
one plane and subtends an angle of 120. The three newly formed hybrid
32
CHM 307 MODULE 1
orbitals will overlap with three p-orbitals (each supply by one atom of
fluorine) to form BeF3. The shape of sp2 molecules is trigonal explaining
why sp2 why sp2 hybridization is sometime called trigonal hybridization.
3.2.1.3 Sp3 hybridization
Sp3 hybridization has 25 % s0character and 75% p-character. It consists

of four hybrid orbitals formed from one s and three p orbitals. The
mixing of the four orbitals takes place in space, hence, the four hybrid
orbitals would also lie in space. An arrangement in space that keeps
them farthest apart is that of a tetrahedron. Consequently, each of the
four hybrid orbitals are directed towards the four corners of a regular
tetrahedron, sp3 hybridization is also called Tetrahedral hybridization.
They are of the same shape as that of the previous two types but bigger
in size. Example of molecule that can accommodate sp3 hybridization is
methane (CH4).
Worked example 3
Explain how carbon combine to form CH4 in spite of the fact that its
electronic configuration suggests that only two bonds can be formed.
Solution
he ground state electronic configuration of carbon is

1 2 2 2 2 . The configuration suggest that carbon can only
form compounds with maximum of two bonds since the configuration
reveal the presence of only two bonding electrons. However, ability of
carbon to form compounds that reveals it tetravalent nature contradict
this principle. The formation of methane involves the promotion of one
electron from 2s orbital into the pz orbital leaving four unpaired
electrons in s, px, py and pz orbitals. These orbitals will mix and form
four hybrid orbitals called sp3 hybrid orbitals and the process is called
sp3 hybridization. The four hybrid orbitals will then overlap with four
hydrogen atoms to form CH4 (see scheme below). Other examples of sp3
hybridized orbitals are found in water and ammonia. In the ammonia
molecule (NH3), 2s and 2p orbitals create four sp3hybrid orbitals, one of
which is occupied by a lone pair of electrons. In a water molecule, two
33
sp3 hybrid orbitals are occupied by the two lone pairs on the oxygen
atom, while the other two bonds with hydrogen.
Scheme for sp3 hybridization in methane
Sp, sp2 and sp3 hybridization is the basic types of hybridization.

However, other types of hybridization involving d-orbitals are sp2d,
sp3d, sp3d2, etc. Fig. 2.2 shows how these hybridizations occur.
Worked example 4
What is the limitation of the valence bond theory?
Solution
The limitations are
(1) The presence of other nuclei should affect the electronic

arrangement of all the atoms in the molecule. The valence bod
theory does not take this into account but concentrates only on
the valence electron
(2) Sometimes a single electronic structure does not explain all
known properties of that molecule or ion and we have the many
electronic structures called resonating structures.
(3) Valence Bond theory fails to explain the bonding in electron
deficient compounds.
(4) It fails to explain the paramagnetic character of compounds such
as oxygen molecule.
34
CHM 307 MODULE 1
Fig. 2.2: Summary of orbitals and orbital arrangement in the three

basic types of hybridization
3.3 Theory of resonance
Theory of resonance in chemistry is a theory by which the actual

normal state of a molecule is represented not by a single valence-bond
structure but by a combination of several alternative distinct structures.
The molecule is then said to resonate among the several valence-bond
structures or to have a structure that is a resonance of these structures.
The energy calculated for a resonance hybrid is lower than the energies
of any of the alternative structures; the molecule is then said to be
stabilized by resonance. The difference between the energies of any one
of the alternative structures and the energy of the resonance hybrid is
designated resonance energy
The theory of resonance is based on the fundamental principle of

quantum mechanics, which states that the wave function representing a
stationary state of a system can be expressed as a weighted sum of the
wave functions that correspond to several hypothetical structures for the
system and that the proper combination is that sum which leads to a
minimum calculated energy for the system.
35
There is sometimes an ambiguity in the location of double bonds. This

ambiguity is illustrated by the Lewis structure for ozone (O3). The
following are two possible structures:
In such cases, the actual Lewis structure is regarded as a blend of these

contributions and is written:
The blending together of these structures is actually a quantum

mechanical phenomenon called resonance, which will be considered in
more detail below. At this stage, resonance can be regarded as a
blending process that spreads double-bond character evenly over the
atoms that participate in it. In ozone, for instance, each oxygen-oxygen
bond is rendered equivalent by resonance, and each one has a mixture of
single-bond and double-bond character (as indicated by its length and
strength).
3.4 Walsh’s rule
Walsh’s rule was developed by Prof. A. D. Walsh while attempting to

explain the explain Mulliken theory on the shapes polyatomic molecules
can adopt in ground and excited states. He found that the shape
polyatomic molecule adopts in their ground state depends on the number
of valence electron.
The formation of molecule maybe seen as a compromise between the
donation and acceptance of electron. This implies that molecular energy
for the donation and acceptance of electron may vary slightly. The
frontier molecular orbital theory identifies two molecular orbital
energies, namely the energy of the highest occupied molecular orbital
(HOMO) and that of the lowest unoccupied molecular orbital (LUMO).
The theory further states that the formation of molecules involves
interaction between the HOMO and the LUMO.
Walsh rule is a rule for predicting the shape of a molecule and states that
a molecule will adopt a structure that best provide the most stability of
its HOMO. This implies that if a structural change does not perturb the
HOMO, the closest occupied molecular orbital governs the orientation
of that geometry.
Walsh diagram (also called angular coordinate diagram or correlation
diagram) can be drawn through single point calculations using
computational software such as Hyperchem, Gaussian, ORCA, etc. The
first step is to carry out geometry optimization (i.e finding the most
36
CHM 307 MODULE 1
stable state of the molecule-ground state). Single point calculations

[(i.e., calculation of potential energy surface (PES). PES describe the
energy of a system as a function of one or more parameter (such as bond
length)]. Further calculations are repeated for various geometries
developed from the optimized geometry through alteration of bond angle
(while bond length is fixed). The Walsh diagram is plotted as a plot of
molecular binding energy versus bond angle. Fig. 2.3 shows the Walsh
diagram for HAH molecule.
Fig. 2.3: Walsh diagram for HAH

(Source: https://en.wikipedia.org › wiki › Walsh diagram)
Worked example 5
What are the application and limitation of Walsh diagram?
Solution
Walsh diagram has some applications as follow,
(i) Walsh diagram can explain why molecules are more stable in
certain spatial configuration. For example, it can explain why
water molecule prefer bent configuration. For molecules having
similar valency,
37
(ii) Walsh diagram can be used to explain observed regularity. The

diagram also provide explanation for observe changes in
geometric of a molecule with changes in valency or spin state.
(iii) In conjunction with the molecular orbital theory, Walsh
diagram can be used to predict the reactivity of a molecule
One of the major setbacks of Walsh diagram is that only the valence
orbitals are considered because the core orbital usually has low energy.
However, some of the valence orbital are not considered, hence the
model may fail in some cases.
Other correlation diagrams commonly used are Tanabe-Sugano and

Orgel correlation diagram but Walsh seems to be the most popular
correlation diagram.
3.5 Molecular orbital theory (MOT)
The MOT was proposed by Hund and Mulliken in 1932 and explain the
formation of molecular orbital through the combination of individual
atomic orbitals with each other. The theory explains that the formation
of molecule considers that the combining electrons in the atomic orbitals
do not belong to a particular bond but spread throughout the entire
molecule. According to the MOT, a molecular orbital is a system
constructed from linear combination of atomic orbitals. This
combination give rise to two main types of orbitals (i.e. the bonding and
anti-bonding molecular orbitals). The bonding molecular orbital arises
from the constructive overlaps of neighbouring atomic orbitals while
anti bonding molecular orbital arises from the destructive overlap of
neighbouring atomic orbitals.
3.5.1 Linear combination of atomic orbital (LCAO)
Linear combination of atomic orbital provides a theoretical approach of

using the wave function to represent the formation of molecular orbital
through appropriate atomic orbitals. If a wave function for a 1S electron
belonging to an atom, A is ( ) ( ) and ( ) ( ) describes the wave
function for a 1s electron found in atom B. The overall wave function
for the system must be written as a superposition of the two atomic
orbitals (equation 2.1),
 = [( ) ( ) + ( ) ( ) 2.1
where N is the normalization factor. The wave function resulting from
superposition of different atomic wave function (as expressed in
equation 2.1) is called linear combination of atomic orbital (LCAO). An
approximate molecular orbital formed from a LCAO is called linear
38
CHM 307 MODULE 1
combination of atomic orbital-molecular orbital (LCAO-MO).

According to the Schrodinger model, the square if the wave function
(i.e., || ) represents the probability density. Therefore, the probability
density of the LCAO-MO of a 1s -orbital can be written as,
|| = ( )
( ) + ( )
( ) 2.2
= ( ) ( ) + ( ) ( ) + 2( ) ( )( ) ( )
2.3
Equation 2.10 has three components which can be explained as follows.
i. ( ) ( ) , which represent the probability density of

electron confined to the orbital, A.
ii. ( ) ( ) , which represents the probability density of
electron confined to the orbital, B.
iii. 2( ) ( )( ) ( ), which is the extra contribution to
the density of electron and is called overlap density.
The overlap density also represents an enhancement of the probability of

finding electrons in the internuclear region above what it would be if
they were confined to one of the two atoms. This enhancement is also
called constructive interference of the two atomic orbitals. Similar
analogy can be extended to antibonding molecular orbital. The
expression representing the formation of antibonding molecular orbital
arising from combination of atomic orbitals of atoms A and B can be
written as,
, = [( ) ( ) − ( ) ( ) 2.4
LCAO-MO for the above wave function correspond to a molecular
orbital having energy higher than any of the contributing orbitals.
Therefore, antibonding molecular orbital increases the energy of a
system Whereas bonding molecular orbital is associated with
constructive interferences, antibonding molecular orbital is associated
with destructive interference. The probability function of antibonding
molecular orbital can also be derived as it was done for bonding
molecular orbital, hence we have
|, | = ( )
( ) − ( )
( ) 2.5
= ( )
( ) + ( )
( ) − 2( )
( ) ( )( )
2.6
It can be seen that the first two terms in equation 2.6 are the same as in
those obtained for bonding molecular orbital and their significant is the
same. However, the difference is in the sign of the third term, which is
positive for bonding molecular orbital and negative for antibonding
39
molecular orbital. The negative value (i.e. [−2( ) ( )( ) ( )] clearly

signify the factor that contribute to reduce the probability of finding
electron between the nuclei. Antibonding orbital raises the energy of the
molecule relative to the separated atom and destabilizes the molecule
relative to the separated atoms whereas bonding electron stabilizes the
molecule.
A combination of N number of atomic orbitals will yield N number of

molecular orbitals. There are two types of molecular orbitals, including
binding and antibonding molecular orbitals. Several combinations of s
or p electron can form bonding or antibonding molecular orbital. The
formation of these molecular orbitals involves combination of valence
electrons in the respective atomic orbitals. For example, combination of
two hydrogen atoms to form hydrogen molecules involves two 1s-
electrons combining with each other as shown below.
The wave functions either have (+) or (–) sign. The positive sign shown
on 1s orbitals of hydrogen atoms reveals that these orbitals are
spherically symmetrical and their wave functions are associated with
+ve sign in all directions. In case of p-orbitals one lobe has +ve sign
while other has –ve sign. The overlapping of atomic orbitals takes place
if they have similar signs on their lobes
The combination generates two set of molecular orbitals. The first is

called sigma bonding molecular orbital i.e. (1s) and sigma antibonding
molecular orbital, *(1s). As can be seen in the above diagram, *(1s)
molecular orbital is positioned at a higher energy level than the (1s)
molecular orbital. This confirms that the bonding molecular orbital
contributes to the lowering of the energy of a molecule and hence
stabilizes the system while the antibonding molecular orbital increases
the energy of the system and thus tend to destabilize the system. A
sigma () electron is an electron that occupies a sigma orbital. Sigma
orbitals can also be formed from combination of pZ orbitals (z is
assumed to be the internuclear axis) as shown in the diagram below,
40
CHM 307 MODULE 1
Apart from sigma orbitals, PY and Px orbitals can combine to give pi-
bonding and pi antibonding molecular orbitals as shown below,
From the above, π(2py) is pi bonding molecular orbital and is formed

when similar charges on the 2py orbitals meet side by side while π*(2p y)
(that is the pi anti bonding molecular orbital) is formed when the
adjacent charges are not similar. Since Px and Py sub orbitals are
degenerate orbitals because they have similar energy, bot bonding or
antibonding molecular orbitals arising from them will also be
degenerate. The π(2py) and π(2px) bonding molecular orbitals have zero
electron density on the plane that contain the nuclear axis but the
electron density is concentrated above and below the nodal region. The
π* (2Py) and π* (2Px) antibonding molecular orbitals have higher energy
than their corresponding molecular and atomic orbitals.
It can be stated that different molecular orbitals have different energy

level. For example, the energy of bonding molecular orbital varies in the
following order, (1s) (2s) (2pZ) π(Py)π(Px) while the order for the
antibonding molecular orbital is *(1s)*(2s) *(2pZ) π(*Py) π*(Px).
However, π(*Py) and π*(Px) are degenerate orbitals just like π(P y) and
41
π(Px) orbitals. The diagram below presents a pictorial trend for the
variation of energy of the bonding and nonbonding molecular orbitals.
s and PZ orbital can combine end to end to form sigma bonding and
sigma antibonding molecular orbitals as shown below
However, s-orbital cannot form a sigma molecular orbital with Py or Px

because they do not have the same symmetry about the internuclear axis.
42
CHM 307 MODULE 1
Generally, the following conditions must be fulfilled before molecular

orbitals can be formed,
(i) The energies of the combining atomic orbitals should be
comparable. For homonuclear diatomic molecules similar atomic
orbitals combine to form molecular orbitals. For example, 1s
from one atom can combine with 1s atomic orbital from another
atom to form molecular orbital. However, Is cannot combine with
2s because the energy is not comparable
(ii) Overlap between atomic orbitals should be considerable

significant. The greater the overlap between the atomic orbitals,
greater is charge density between the nuclei.
(iii) The symmetry of the combining atomic orbitals should be the
same. The atomic orbitals should have the same symmetry about
the internuclear axis. For example, 2s orbital of one atom can
combine with 2s or 2Pz orbital of another atom but not with the
2Py or 2Px orbital. Molecular orbitals that can be formed from
combination of possible atomic orbitals are presented in the Table
2.1 below,
Table 2.1: Combination of atomic orbitals and their corresponding

molecular orbitals
Atomic orbital 1 Atomic orbital 2 Molecular orbital

s-orbital s-orbital  (sigma) orbital
s-orbital PZ orbital  (sigma) orbital
PZ orbital PZ orbital  (sigma) orbital
Px orbital Px orbital π (pi) orbital
Py orbital Py orbital π (pi) orbital
The formation of bonding molecular orbital can be viewed as addition of

electron waves (i.e. constructive interference) while the formation of
antibonding molecular orbital is a product of subtraction of electron
wave. Fig. 2.4 shows the variation of molecular energy with internuclear
distance for both bonding and antibonding molecular orbital. The
distance corresponding to the minimum of the curve for bonding
molecular orbital is the equilibrium bond length (re) and the
corresponding energy is the dissociation energy (De). For example, the
theoretical values of re and De for hydrogen molecular ion are 130 pm
and 1.77 eV respectively.
43
Fig. 2.4: Variation of energy with R for bonding and antibonding

molecular orbital
Repulsive forces dominate during the formation of an antibonding

molecular orbital. However, during the formation of a bonding
molecular orbital the energy starts decreasing and reaches to a minimum
value which corresponds to the bond length between the two atoms (r0).
At a distance less than r0 the repulsive forces start dominating over the
attractive forces and energy starts increasing
The term bond order (b) is often use to predict the stability of a
molecule. Bond order, b is defined as half the difference between the
number of electrons in the bonding molecular orbital (n) and the
electrons antibonding molecular orbital (n*). That is b = ½ (n = n*). The
greater the bond order, the more stable is the compound. Generally,
bond order greater than unity points toward stability whereas bond order
less than unity points toward instability.
Apart from the s-electrons described above, p-electrons also contribute

to the formation of molecular orbital. P-orbital has three degenerate
orbital (Px, Py and Pz) which are perpendicular to each other and can
overlap constructively or destructively giving rise to pi (π) bonding and
anti-pi (π*) bonding molecular orbitals respectively.
44
CHM 307 MODULE 1
Worked example 6
In a Tabular form, state five differences between bonding and

antibonding molecular orbitals
Bonding molecular orbital Antibonding molecular orbital
The wave function is , = [( ) ( ) − The wave function is , = [( ) ( ) −
( ) ( ) ( ) ( )
Form from constructive (or addition) overlap Formed from destructive(subtraction)
of atomic orbitals overlap of atomic orbitals
Formed when the lobes of atomic orbitals Formed when the lobes of atomic orbitals
have same signs have different signs
Energy is lower than that of the combining Energy is higher than that of the combining
atomic orbitals atomic orbitals
The electron density is high in the region Electron density is low in the region between
between the nuclei of bonded atoms the nuclei and bonded atoms
Every electron in bonding MO contributes Electrons in antibonding molecular orbital
towards the attractive force contributes to repulsive force
Stabilizes the molecule Destabilizes the molecule
Solution
The strength of a chemical bond depends to some extent, on the nature

of orbital overlap. Strong bonds results from combination of orbitals that
have similar or nearly similar energies. In homonuclear diatomic
molecule, the energy of the 2S orbital of the two atoms are the same and
so is the energy of the 2P orbitals of the two atoms. Therefore, the 2S
orbital will formed a strong overlap and so will the 2P orbital also yield
strong overlap because the respectively orbitals, which have similar
energies. These overlaps will contribute to a sigma orbital. It is the
convention of quantum mechanics to write a sigma orbital in terms of all
the orbitals that have symmetry to contribute to the final orbital. This is
represented in equation 2.7
 = ( ) ( ) + ( ) ( ) + ( ) ( ) +
( ) ( ) 2.7
where Cs are the various orbital coefficient.
Worked example 7
(a) In a Tabular form, state four differences between sigma and Pi

molecular orbitals
(b) What is common between pi and sigma molecular orbitals
45
Solution
(a)
Sigma molecular orbital Pi molecular orbital

Formed by head to head Formed by sideward overlapping
overlapping of atomic orbitals. of Px or Py atomic orbitals
The overlap is along internuclear Overlap is perpendicular to
axis. internuclear axis
This orbital is symmetrical to Orbital is not symmetrical to
rotation about the line joining the rotation about the line joining the
two nuclei. two nuclei.
The region of overlap is greater Region of overlap is less resulting
leading to the formation of strong in the formation of weak bond.
bond
(b) The common feature is that they are both formed from proper
combination of atomic orbitals, leading to the formation of
overlap.
3.6 Bond order
The term bond order (b) is often use to predict the stability of a
molecule. Bond order, b is defined as half the difference between the
number of electrons in the bonding molecular orbital (n) and the
electrons in the antibonding molecular orbital (n*). That is b = ½ (n =
n*). The greater the bond order, the more stable is the compound.
Generally, bond order greater than unity points toward stability whereas
bond order less than unity points toward instability. Let us calculate
bond order of some molecules as shown below,
Worked example 8
Apply the molecular orbital theory to explain bonding in the following

molecules
(i) Hydrogen molecule

(ii) Helium molecule
(iii) Oxygen molecule
In each case, calculate the bond order and comment on the result
obtained from the calculation
46
CHM 307 MODULE 1
i. Hydrogen molecule
Hydrogen molecule has two electrons, each contributed by 1s orbital.

According to the Aufbau principle, the lowest level must first be filled
before the higher level. The molecular orbitals formed between the two
hydrogen atomic orbitals are sigma bonding and sigma antibonding
molecular orbitals,
(1 ) + (1 ) → ∗
(1 ), (1 )
Consequently, the number of electrons in bonding molecular orbital is

two while the number in antibonding molecular orbital is zero.
Therefore, the bond order of hydrogen molecule is
∗
− 2−0
( )= = =1
2 2
The calculated bond order indicate that two hydrogen atoms are bonded
together by only one bond to form hydrogen molecule. The formation
process can be represented as shown in the diagram below,
ii. Helium
Helium has atomic number of two, hence two electrons. When two
helium atoms combine, four electrons will be formed. The molecular
orbital formed is developed from combination of two 1s atomic orbitals.
That is a total of two molecular orbitals would be formed Thus
(1 ) + (1 ) → ∗
(1 ), (1 )
Therefore, the bond order for helium is
− ∗ 2−2
( )= = =0
2 2
47
Calculated bond order of zero indicate that the molecule cannot exist.
iii. Oxygen molecule
The electronic configuration of oxygen is 1 2 2 2 2 . In this

case, only the 2s and 2p orbitals would be involved in bonding (i.e.
valence shell) giving a total of five electrons for each contributing
oxygen atom and 6(2) =12 for the oxygen molecule. The equation can
be written as,
)
(1 2 2 2 2 + (1 2 2 2 2 )
∗ (2 ) ∗ 2 ∗( )
→ (2 ) (2 ) (2 ) 2 2
From the molecular orbital configuration is

∗ (2 ) 2 ∗ ∗ (2 ) indicating that
(2 ) (2 ) (2 ) 2
the number of bonding electron is 8 while the number of antibonding
electron is 4 (see diagram below). Therefore, the bond order is
∗
− 8−4
( )= = =0
2 2
The calculated bond order of 2 indicate that oxygen molecule is stable

(n>n*) and from the above diagram, there are unpaired electrons hence
it is paramagnetic.
48
CHM 307 MODULE 1
Worked example 9
(a) Calculate the bond order of nitrogen molecule from first principle.
Also present a diagram to indicate how the bonding electrons are
distributed. Is the molecule stable? Give reason for your answer. (b) Is
N2 paramagnetic or diamagnetic. Give reason for your answer.
Solution
(a) Nitrogen atom has seven electrons and its electronic configuration is
1 2 2 2 2 indicating that the valence shell configuration is
2 2 2 2 . This gives five electrons and a total of ten electrons (i.e.
2 x 5=10) when they combine with one another. The formation of
molecular orbital occurs according to the following equation,
+
→ (2 ) ∗ (2 ) (2 ) 2 (2 ) ∗ 2 ∗(
2 ) ∗ (2 )
In this case the number of bonding electrons is eight (8) while the
number of nonbonding electrons is four (4). Therefore, the bond order is
− ∗ 8−2
( )= = =3
2 2
The molecule (N2) is stable because the bond order is positive. i.e. n>n*.
A diagram showing the distribution of electrons into the various bonding
and antibonding orbitals is shown below
49
(b) From the above diagram, it can be seen that N2 is diamagnetic

because all the electrons are paired
Worked example 10
Show from first principle that beryllium cannot exist as a molecule
Solution
Beryllium is the fourth element in the periodic Table. It has four

electrons indicating that its electronic configuration is 1 2 . This
means eight electrons will be used for the formation of molecular orbital
(i.e. each atom contributes 4). Consequently, the formation of molecular
orbital will take place according to the following equation
+ → (2 ) ∗ (2 ) (2 ) ∗ (2 )
From the above, the number of bonded electrons is 4 while the number
of nonbonding electrons is also equal to 4. Hence the bond order is
∗
− 4−4
( )= = =0
2 2
Since the calculated bond order is xero, Be2 does not exist
Worked example 11
50
CHM 307 MODULE 1
What are the four major information that can be deduced from bond
order of a molecule
Solution
(1) Stability of the Molecule/Ion: A molecule/ion is stable if n > n*,

i.e. when the bond order is positive. However, when the bond
order is negative, the molecule is not stable and when the bond
order is zero, the molecule does not exist.
(2) Bond Dissociation Energy The greater the bond order, the greater
is the bond dissociation energy.
(3) Bond Length Bond order is inversely proportional to bond length.
Bond length increases as the bond order decreased.
(4) Magnetic Properties The presence of unpaired electrons in
molecular orbitals of a species makes it paramagnetic in nature.
Greater the number of unpaired electrons, the more will be its
paramagnetic character. On the other hand, if there are no
unpaired electrons in the species will be diamagnetic in nature.
3.7 Bond order for heteronuclear diatomic molecule
Heteronuclear molecules are formed from combination of two dissimilar

atomic orbitals. This means each atomic orbital contributes unevenly to
the molecular orbital. The wave function for the molecular orbital of
heteronuclear diatomic molecule can be written as
 =  + 
In developing molecular orbitals for heteronuclear molecule, the
bonding molecular orbital is made close to electronegative atom while
the antibonding molecular orbital is close to the electropositive atom. A
common example of hetero nuclear diatomic molecule is NO. The
molecule is formed from N and O. Their electronic configuration is,
= 1 2 2 2 2
= 1 2 2 2 2
The number of valence electron in nitrogen is 5 and 6 for oxygen. This

gives a total of 11 valence electrons. The configuration of molecular
orbital of NO can be written as,
+ → (2 ) ∗ (2 ) (2 ) 2 (2 ) ∗ 2
The total number of bonded electrons is 8 while the total number of
nonbonding electrons is 3. Therefore, the bond order for NO is
∗
− 8−3
( )= = = 2.5
2 2
51
Molecular orbital diagram is shown below
From the above, NO is stable because n>n*. No is paramagnetic because

not all its electrons are paired.
3.8 Theory of bonding in some systems
3.8.1 Theory of bonding in hydrogen molecular ion
Under the MOT treatment, the hydrogen molecular ion is the simplest
molecule that can be considered. In the MOT approach, the formation of
molecule is pictured as situation in which the combining electron do not
belong to a particular bond but spread throughout the entire molecule.
Consequently, according to the MOT, a molecular orbital is a system
constructed from linear combination of atomic orbitals, which results in
two main types of orbitals (i.e. the bonding and anti-bonding molecular
orbitals). The bonding molecular orbital arises from the constructive
overlaps of neighbouring atomic orbitals while anti bonding molecular
orbital arises from the destructive overlap of neighbouring atomic
orbitals. This approach can be simplified by considering two nuclei, A
and B separated by a distance, R as shown Fig. 2.5.
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CHM 307 MODULE 1
. . : ( )
The Hamiltonian for this system can be written as follows,

ћ ћ
= + + + = ∇ + 2.8
The force of attraction arising from interaction between electron and the
nuclei will be inversely proportional to the distance of separation and is
given by,
+
2.9
On the other hand, the repulsive interaction between the nuclei is given
as,
×
2.10
The potential energy of the system will be the sum of the forces of
attraction and repulsion as expressed in equation 2.11
= + +
2.11
Substituting for U in equation 2.8, equations 2.12 and 2.13 are obtained,
ћ
= + + − + +
2.12
ћ
= ∇ − + +
2.13
Equation 2.13 can further be inserted into the Schrödinger equation to
obtained equation 2.14, which expresses the Schrödinger equation for
hydrogen molecular ion,
ћ
∇ − + +  = 
2.14
53
The one electron wave function obtained by solving the Schrödinger

equation is called molecular orbital. A molecular orbital is significant
because through the function, || , it gives the probability of finding
electron in the molecule.
Worked example 12
Consider two atomic nuclei (A and B) separated from each other by a

distance equal to R. If the distant of A and B from electron are ra and rb.
Answer the following questions
i. Write an expression for the Hamiltonian of the system

ii. What is the force of attraction and repulsion for this system?
iii. Write an expression for the potential energy of the system
iv. Write expression for the Schrodinger equation of this system
From your results, define the term, molecular orbital and state its
significant
Solution
i. The Hamiltonian for this system can be written as follows,

ћ ћ
= + + + = ∇ + 1
ii. The force of attraction arising from interaction between
electron and the nuclei will be inversely proportional to the
distance of separation and is given by,
+
2
On the other hand, the repulsive interaction between the nuclei is
given as,
× 3
iii. The potential energy of the system will be the sum of the
forces of attraction and repulsion as expressed in equation 4
= + + 4
Substituting for U in equation 1, equations 5 and 6 are obtained,
ћ
= + + − + + 5
ћ
= ∇ − + + 6
iv. Equation 6 can further be inserted into the Schrödinger equation

to obtained equation 7, which expresses the Schrödinger equation
for hydrogen molecular ion,
54
CHM 307 MODULE 1
ћ
∇ − + +  = 
7
The one electron wave function obtained by solving the Schrödinger

equation is called molecular orbital. A molecular orbital is significant
because through the function, || , it gives the probability of finding
electron in the molecule.
3.8.2 Theory of bonding in hydrogen atom
The potential energy for the hydrogen atom can be written as,
−
=
4
The expression does not contain the Cartesian coordinate (i.e. xyz) but r
which is a spherical polar coordinate. The task of simplifying the
therefore entails, conversion of the Cartesian coordinate to the polar
coordinate. While the Cartesian coordinate deals with xyz, the polar
coordinate in this case will also involves three parameters, namely, r, 
and . The relationship between r and the Cartesian system can be
written as,
= + +
= + +
In spherical polar coordinates, r is the length of the radius vector from
the origin to a point (xyz). In order to present analytical solution, let us
consider a system involving both the polar and the Cartesian coordinate
as shown in Fig. 2.6,
Fig. 2.6: Coordinate of hydrogen atom
55
The angle between the z axis and the radius is  while the angle between
projection of the radius vector onto the xy plane and the +x axis is given
as , From the diagram,
= =
+ +
=
+ +
=
Consequently, = sin , = sin sin = /

The Schrödinger equation can be written as,
   2
+ + + ( − ) = 0
ћ
In spherical polar coordinate the Schrödinger equation becomes,
  
+ + + ( − ) = 0
ћ
When the potential energy is introduced, the equation becomes,
  
+ + + +  =0
ћ
Worked example 13
i. Write expression for the potential energy of hydrogen atom.

What is the shortcoming of the equation if it is to be used for
solving the Schrodinger equation for the hydrogen atom?
ii. How can you overcome the challenges?
iii. Use the diagram below to derive the relationship between polar
and cartesian coordinate system for hydrogen atom
56
CHM 307 MODULE 1
Solution
i. The potential energy for the hydrogen atom can be written as,
−
=
4
The expression does not contain the Cartesian coordinate (i.e. xyz) but r
which is a spherical polar coordinate.
ii. The task of simplifying the therefore entails, conversion of the

Cartesian coordinate to the polar coordinate. While the Cartesian
coordinate deals with xyz, the polar coordinate in this case will
also involves three parameters, namely, r,  and . The
relationship between r and the Cartesian system can be written as,
= + +
= + +
ii. In spherical polar coordinates, r is the length of the radius vector
from the origin to a point (xyz). In order to present analytical
solution, let us consider a system involving both the polar and the
Cartesian coordinate as shown in Fig. 2.6,
The angle between the z axis and the radius is  while the angle between
projection of the radius vector onto the xy plane and the +x axis is given
as , From the diagram,
57
= =
+ +
=
+ +
=
=
Consequently, = sin , = sin sin = /
The Schrödinger equation can be written as,
3.8.3 Theory of bonding in helium atom
Helium atom has atomic number of two (Z = 2) and a mass of 4. The

Bohr’s theory fails to solve problems be young the hydrogen atom.
However, it has been found that the approximation method gives
solution that significantly agrees with experimental data. We can
consider ground and excited state of helium as follows,
+ + 2
IE1 is the minimum energy required to remove one electron from helium
atom in its ground state (i.e. first ionization energy). It is numerically
equal to 25.49 eV. The second ionization energy may be calculated
using the following equation.
= − ( )= =2 = 54.42
2
By definition, the ground state energy of helium atom can be calculated

using the following equation,
= −( + ) = −79.02 = 2.90372
The Schrodinger equation for the helium atom can be written as,
1 1 1
− ∇ − ∇ − + ( , ) = ( , )
2 2
The first term in the Hamiltonian expression is the kinetic energy of

electron 1, the second is the kinetic energy of electron 2, the third is the
nuclear attraction of electron 1 and 2 and the last is the repulsive
interaction between the two electrons. Finding exact solution for helium
atom problem is complicated by the repulsive interaction term (i.e.
1/r12). Therefore, in order to solve the Schrodinger equation for the
ground state helium atom, the problem is solved with the other terms
(excluding the repulsive term). This approach is called neglect of
electron repulsion. After solving, the last term is re-introduced. The
58
CHM 307 MODULE 1
variables, r1 and r2 can be separated for the helium atom such that it will
take the form of two separate hydrogen like atom wave function as
follows,
( )
 ( , ) =  ( ) ( ) =
The ground state energy of helium atom obtained from the above
equation can be calculated from the equation, 2 × . This gives a
theoretical value of -4 Hatree s opposed to the experimental value of -
2.90 Hatree. Thus, neglect of electron repulsion can introduce a very
large error. This error can be reduced by using a functional form of the
wave function, which replaces Z with adjustable parameter, α. The new
equation now becomes,
( )
 ( , ) =  ( ) ( ) =
If the above function is used in the variational equation, we have,

∫  ( ) ( )  ( ) ( )
=
∫  ( ) ( ) ( ) ( )
The Hamiltonian in the equation is the full Hamiltonian, which include

the repulsive term (1/r12). Consequently, the expectation value of the
first part of the Hamiltonian generates the following expression,
1 1
〈− ∇ 〉 = 〈− ∇ 〉 =
2 2 2
〈 〉= 〈 〉 = ,〈 〉=
The variational energy is obtained by summing all the integers in the

above equation as follows,
5
( ) = + 2 +
8
In order to account for the upper bound, we must find the optimal value
of , which minimise the variational energy. This is done by
differentiating the above expression with respect to . This gives,
5
=2 +2 +
8
From the above, the optimum value of the above parameter is obtained
when = 0, consequently,
5
2 +2 + =0
8
59
5
= −
16
Hence,
5 5 5 5 5
( ) = + 2 + = − +2
+ −
−
8 16 16 8 16
5 5 5
( ) = − − +2 +
16 16 8
Since 2 + 2 + = 0, 2 + = 2 . Hence the above equation
simplifies t0
5 5
( ) = − − −2
16 16
5 5 5
( ) = − − −2 −
16 16 16
5 5
( ) = − − −
16 16
5
( ) = − −
16
The variational energy obtained from the above equation is numerically
equal to -2.84775 Hatree, while the experimental value is -2.90572
Hatree. This is a good approximation with an error margin of only 2%.
Other methods that have been found useful for approximating the
ground state energy of helium atom are presented in Table 1.
Table 2.1: Estimated theoretical ground state energy of helium atom
Wavefunctions Parameters Energy

( ) Z=2 -2.75
( ) α = 1.6875 -2.84765
(r1)(r2) best (r) -2.86186
( ) best α, c -2.89112
(1 + cr12)
Hyleraas (1929) 10 parameters -2.90363
Pekeris (1959) 1078 parameters -2.90372
Non-inclusion of the repulsion term variable (r12) can lead to

considerable error. The effect is called electron correlation. The method
that uses the function, (r1)(r2) is called self-consistent field method
and does not include the repulsion term, hence it has considerably error.
The fourth entry, containing a simple correction for correlation, gives a
considerable improvement. Hylleraas (1929) extended this approach
with a variational function of the form,
( )
( , , ) = × , ,
As can be seen in the results, this method gives a strong agreement with
experimental result.
60
CHM 307 MODULE 1
(i) Self-Assessment Exercise
1. What are the similarities and differences between sigma and pi

bond?
2. Identify the number of sigma and pi bond in HCN
3. What is the significant hybridization in valence bond theory?
4. A molecule with the formula AB3 could have one of two different
shapes. Give the shape and the hybridization of the central A
atom for each.
5. Use the following equation to calculate the ground state
vibrational energy of helium,
= −
( ) − . Compare your results with experimental
value and state the error margin.
6. Write ionization equation for helium. Hence define the first
ionization energy of helium. If the first ionization energy of
helium is 25.49 eV, calculate the second ionization energy and
the ground state energy of helium.
7. Write the Schrodinger equation for helium atom and define all
the terms in the equation. Which of the term can complicate the
solution to the helium atom problem?
8.
a. Write an expression for the probability density of linear
combination of atomic orbital molecular orbital of a 1s -orbital.
Hence, use the equation to deduced all the probabilities
associated with the LCAO-MO.
b. Write an expression for the probability density of linear
combination of atomic orbital molecular orbital of a 1s *-
orbital. Hence, use the equation to deduced all the probabilities
associated with the LCAO-MO
Answer to Self-Assessment Exercise
1. Similarities: Both types of bonds result from overlap of atomic

orbitals on adjacent atoms and contain a maximum of two
electrons. Differences: σ bonds are stronger and result from end-
to-end overlap and all single bonds are σ bonds; π bonds between
the same two atoms are weaker because they result from side-by-
side overlap, and multiple bonds contain one or more π bonds (in
addition to a σ bond).
2. HCN has two σ (H–C and C–N) and two π (making the CN triple
bond).
3. Hybridization is introduced to explain the geometry of bonding
orbitals in valance bond theory.
4. trigonal planar, sp2; trigonal pyramidal (one lone pair on A) sp3
61
5. The variational energy obtained from the above equation is

numerically equal to -2.84775 Hatree, while the experimental
value is -2.90572 Hatree. This is a good approximation with an
error margin of only 2%.
6. The equation for ionization of helium is +
+ 2
IE1 is the minimum energy required to remove one electron from
helium atom in its ground state (i.e. first ionization energy). It is
numerically equal to 25.49 eV. The second ionization energy may
be calculated using the following equation.
= − ( )= =2 = 54.42
2
By definition, the ground state energy of helium atom can be
calculated using the following equation,
= −( + ) = −79.02 = 2.90372
7. The Schrodinger equation for the helium atom can be written as,
1 1 1
− ∇ − ∇ − + ( , ) = ( , )
2 2
The first term in the Hamiltonian expression is the kinetic energy
of electron 1, the second is the kinetic energy of electron 2, the
third is the nuclear attraction of electron 1 and 2 and the last is the
repulsive interaction between the two electrons. Finding exact
solution for helium atom problem is complicated by the repulsive
interaction term (i.e. 1/r12).
8. a. The 1s -orbital is a bonding molecular orbital. Therefore,
the probability density of the LCAO-MO of a 1s -orbital
can be written as,
|| = ( )
( ) + ( )
( ) 1
= ( ) ( ) + ( ) ( ) + 2( ) ( )( ) ( )
2
Equation 2 has three components which can be explained as follows.
i. ( ) ( ) , which represent the probability density of

electron confined to the orbital, A.
ii. ( ) ( ) , which represents the probability density of
electron confined to the orbital, B.
iii. 2( ) ( )( ) ( ), which is the extra contribution to
the density of electron and is called overlap density.
The overlap density also represents an enhancement of the probability of

finding electrons in the internuclear region above what it would be if
they were confined to one of the two atoms.
62
CHM 307 MODULE 1
b. The 1s *-orbital is an antibonding molecular orbital, therefore

the LCOA-MO for this system is
, = [( ) ( ) − ( ) ( ) 3
LCAO-MO for the above wave function correspond to a molecular

orbital having energy higher than any of the contributing orbitals.
Therefore, antibonding molecular orbital increases the energy of a
system Whereas bonding molecular orbital is associated with
constructive interferences, antibonding molecular orbital is associated
with destructive interference. The probability function of antibonding
molecular orbital can also be derived as it was done for bonding
molecular orbital, hence we have
|, | = ( )
( ) − ( )
( ) 4
= ( )
( ) + ( )
( ) − 2( )
( ) ( )( )
5
It can be seen that the first two terms in equation 5 are the same as in
those obtained for bonding molecular orbital and their significant is the
same. However, the difference is in the sign of the third term, which is
positive for bonding molecular orbital and negative for antibonding
molecular orbital. The negative value (i.e. [−2( ) ( )( ) ( )] clearly
signify the factor that contribute to reduce the probability of finding
electron between the nuclei.
4.0 CONCLUSION
Molecular orbital theory, hybridization and valance bond theories are

the major theories that describes bonding in molecules. Although these
theories have been widely applied to explain several binding, each of
them is enveloped with some limitation indicating, a compromise for the
best theory in explaining bonding in molecule depends on the nature of
the molecule.
63
5.0 SUMMARY
A molecule is quite different from its constituent atoms and all the
electrons belongs to the constituent atom and are considered to be
moving under the influence of all nuclei.
Atomic orbitals of individual atoms combine to form molecular orbitals

and these MOs are filled up in the same way as atomic orbitals are
formed. In other words, Pauli’s exclusion principle, Aufbau principle
and Hund’s rule of maximum multiplicity are followed. The molecular
orbitals have definite energy levels and the shapes of MOs formed
depend upon the shape of combining atomic orbitals.
Quantum chemistry can adequately predict the ground state energy of

helium when the repulsion interact ion term is properly accounted for
the right model
(1) Use appropriate theories to explain bonding in O2, HCN and H2

(6 minutes)
(2) What are the advantage of molecular orbital theory over valence
bond theory (4 minutes)

Aruldhas (2007). Molecular structure and spectroscopy. Prentice Hall of
India




Publishing, UK

64
CHM 307 MODULE 1





Struve, W. S. (1987), Fundamental of molecular spectroscopy Springer



.
65
CHM 307 MODULE 2
MODULE 2
UNIT 1 MOLECULAR SPECTROSCOPY
CONTENT
1.0 Introduction
2.0 Intended Learning Outcome
3.0 Main Content
3.1 Dipole Moment and Interaction of Radiation with Matter
3.2 Vibrational Energy
3.2.1 Simple Harmonic Motion
3.3 Rotational Energy
3.3.1 Semi Rigid Rotor
3.3.2 Centrifugal distortion
3.4 Rovibrational Energy
3.5 Electronic Energy
(ii) Class Activity
5.0 Conclusion
6.0 Summary
1.0 INTRODUCTION
Spectroscopy is the study of interaction of radiation with matter.

Radiations relevant in spectroscopic study are those that belong to the
electromagnetic spectrum. When any of the component of
electromagnetic radiation (EMR) interact with matter, electron could be
excited or the energy level of the molecule may change through
interaction with proton. Generally, they are two basic types of
spectroscopy, namely,
i. Atomic spectroscopy: In atomic spectroscopic, all transitions are

associated with changes in the configuration of electron.
ii. Molecular spectroscopy: This is associated with changes in the
energy of the molecule and is accompanied by changes in nuclei
vibration and rotation.
Molecular spectroscopy is the study of the absorption or emission of

electromagnetic radiation by molecules. Molecular spectroscopy can be
classified based on the molecular energy that is been altered during
absorption or emission. Consequently, we have rotational, vibrational
and electronic spectroscopy. Rotational spectroscopy is concern with
changes in rotational energy of a molecule. Vibrational spectroscopy
deals with changes in vibrational energy of a molecule while electronic
66
spectroscopy is based on changes in the energy of a molecule due to

different electronic arrangement or re-arrangement.
Internal energy of a molecule defines all the energies a molecule

possesses. These include electronic (Eel), rotational (Erot), translational
(Etran), vibrational (Evib) and other forms of molecular energies (Eothers).
Therefore, we can write the total energy of a system as follows,
= + + + …….. +
In molecular spectroscopy, the significant components of the energy are

rotational, vibrational and electronic energies because below 1000 K, all
other components are negligible. This is consistent with the Born-
Oppenheimer approximation, which account for a steady nucleus
approximation. Therefore, according to this approximation, the total
energy of a molecule can be written as,
= + + 3.1
Also, from Einstein theory, energy is related to frequency, i.e., =
h.Therefore, rotational, vibrational and electronic energy terms are
ℎ , ℎ and ℎ respectively. According to this approximation,
the energy difference associated with excitation of electron (ℎ ) is
much higher than the molecular vibrational energy (ℎ ), which in
turn is higher than molecular rotational energy (ℎ ) because of the
frequencies responsible for the respective transition. The general trend
is,
ℎ >ℎ >ℎ 3.2
Transition between the vibrational energy levels is achieved by infra-red

radiation, transition between rotational energy levels is achieved by far
infra-red and by micro wave radiations while electronic energy levels
transition is achieved by using visible light and ultra violet red
radiations. Therefore, the major components of molecular spectroscopy
are infra-red spectroscopy, UV-visible spectroscopy and micro wave
spectroscopy. Vibrational transition results in changes in rotation of
molecules while electronic transition results in changes in both vibration
and rotation energies of a molecule.
There are also other significant spectroscopy techniques that can also be
used to study molecules. These include nuclear magnetic spin resonance
spectroscopy (NMR) and electron spin resonance spectroscopy (ESR).
The energy levels that are studied under NMR and ESR spectroscopy
are contrary to those studied under rotational, vibrational and electronic
spectroscopy. NMR is based on changes in energy arising from different
in orientation of certain nuclei due to the effect of applied magnetic
field. These different orientations correspond to different energies. This
enable radiation of suitable frequency to be used to study the energy
67
CHM 307 MODULE 2
level separations. In ESR, differences in the orientation of a spinning

electron correspond to different energy level and by using radiation of
suitable frequency, the resulting energy separation can be studied.
The selection rule is a mathematical expression that can be used to know

allowed or forbidden spectroscopic transition. According to the time-
dependent spectroscopic theory, the probability of a molecule to
absorb a light photon is given by the following expression,
← ⌈⟨ | |0⟩⌉ 3.3
where ⟨ | |0⟩ is the matriz element of transition dipole moment. This
factor is related to the Schrödinger wave equation according to the
following equation,
⟨ | |0⟩` = ∫ ∗ 3.4
∗
where and are the molecular wave functions of the initial and
excited states respectively. The total dipole moment is a vector which
can be expressed as,
μ = ∑ 3.5
where qi is the charge of the ith particle and is the radius vector of the
ith particle. The summation is done such that all particles are considered.
From equations 3.4 and 3.5, it can be seen that the rate of transition is
proportional to,
i. and hence the intensity of the incident light

ii. The square of the Z-component of the dipole moment matrix
element, ⟨ | |0⟩
Equation 3.4 also reveals that the matrix element, ⟨ | |0⟩ depends on
the symmetry of both the initial and excited molecular states, which in
turn depends on the quantum number (vibrational or rotational quantum
numbers, as the case maybe). Those quantum numbers that gives the
matrix element a value of zero, presents molecular transition that is
called forbidden transition. On the other hand, those transitions that
results from quantum numbers that gives non zero values lead to
allowed transition and hence transition selection rules.
In molecular spectroscopy, spectral lines originate from emission or

absorption of light. In emission spectroscopy, a molecule returns from a
higher energy level to a lower energy level and emits radiation.
Absorption spectroscopy is concern with the absorption of
monochromatic light that is a function of frequency. The Bohr formula
can be used to presents the energies of the absorbed and emitted
radiation according to equation 3.6,
ℎ = − 3.6
68
where  is the frequency and h are the Planck constant.  is related to

the wavelength,  according to the equation,
 = 3.7

where c is the speed of light. The reciprocal of the wave length is called
wave number and can be written as,

=  = 3.8

Given that N1 represent the population of the first level, i.e., level 1 and
A12 is the Einstein coefficient of spontaneous emission, then applying
the Einstein theory of spontaneous radiation, decay of excited state E1
it can be stated that
= − . 3.9
Re-arranging and integrating equation 3.9, we have equation 3.10 and
3.11 respectively,
( )
∫ = −∫ 3.10
( )
( )
ln = − 3.11a
( )
( ) = ( ) 3.11b
Generally, when monochromatic light passes through a sample, three

possibilities are likely, namely, absorption, transmission, emission or
scattering. The ratio of the transmitted light to the incident light (i.e. I/I0)
is called transmittance (T). According to Beer-Lambert law, the
transmitted light intensity is a function of concentration of the specie (C)
and of the sample path length (l). We can therefore express Beer-
Lambert law as follow,
= 3.12
where k is the absorption cross section, C is the concentration and l are

the path length. Most often, the unit of k is cm2, C is in cm3 and l is in
cm. Since absorption, A is equal to log(Io/I). The, Beer-Lambert law can
be expressed according to equation 3.13,
= = lC 3.13
where  is called molar absorptivity or extinction coefficient or molar

concentration. Therefore, the relationship between absorbance and
transmittance is given according to equation 3.14,
= 3.14
69
CHM 307 MODULE 2
Since %transmittance is equal to transmittance x 100, equation 3.14 can

also be written as
= = 2− 3.15
%
2.0 INTENDED LEARNING OUTCOME
When you have studied this session, you should be able to
 Understand the theory of spectroscopy, its origin and rules

 Understand the dipole moment, various types of dipole and
dipole requirement for transition and spectral observation
 Understand the theory of vibrational spectroscopy and explain the
expansion of a chemical bond in terms of simple harmonic
motion
 Know and apply the selection rule for vibrational spectroscopy
 Know the theory of rotational spectroscopy and derive equation
for rotational energy based on the concept of rigid rotor and
centrifugal distortion.
 Derive and apply selection rule for rotational spectroscopy
 Understand the concept of electronic spectroscopy and its
advantages over other spectroscopic techniques.
 Understand rovibrational spectroscopy and derive equation for
the combined pectroscopies
3.0 MAIN CONTENT
3.1 Dipole moment and interaction of radiation with matter
Spectroscopy employs electromagnetic radiation (including UV and

visible range of radiation) to explored molecular properties. A
consideration of a plane polarized (i.e. linear polarized light) indicates
that it has both electric and magnetic components which are
perpendicular to each other and can be described by the following
equations
= (2 − )
= ( 2 − )
where Ex and Hy are strength of the oscillating electric and magnetic

fields in the x and y directions respectively. The equation reveals that
they are oscillating sinusoidally at a frequency of 2 and since k is the
same for both, the two are in phase. However, interaction of radiation
with matter often occurs through electric component, hence the plane of
polarization is the xy plane containing the direction of E and the
propagation (see Fig. 3.1)
70
Fig. 3.1: Plane polarized light travelling along the x-axis
Stationary states are states that are time independent. If they are two
states (state 1 and state 2), the pair may designate vibrational, rotational
or electronic states. According to classical mechanics, the energy change
when a system is subjected to radiation of frequency, v can be expressed
as,
∆ = − =ℎ =ℎ ̅ 3.16
where ̅ = and since  = c/v, 1/= v/c, hence = ̅ . When radiation

interact with matter, the three things that are possible are induced
absorption, spontaneous emission and induced or simulated emission (as
shown in the diagram below)
Induced absorption occurs when a molecule or atom absorbs radiation

and move from state 1 to state 2, i.e. from lower energy level to higher
energy level. This process can be represented as,
+ℎ ̅ → ∗
When the molecule or atom in the excited state (M*) emits radiation
spontaneously, the process is called spontaneous emission, i.e.
∗
→ +ℎ ̅
As shown in the two equations, spontaneous emission is the reverse of

induced absorption indicating that the quantum of radiation absorbs is
the same as the quantum of radiation emitted.
71
CHM 307 MODULE 2
In stimulated or induced emission, a quantum of radiation is required to

induced spontaneous emission of radiation by the excited molecule. This
can be shown by the following equation,
∗
+ℎ ̅ → + 2ℎ ̅
If the population in states 1 and 2 are N1 and N2, the rate of change of
population due to induced absorption is given as,
= ( ̅) 3.17
where B12 is the Einstein coefficient, ( ̅ ) is the spectral radiation

density and is given as,
( ̅) = 3.18
( / )
In the same way, induced emission changes the population by

= − ( ̅) 3.18
B21 is the Einstein coefficient for the process. B12 = B21. Consequently,
the rate of change of the population N2 gives spontaneous emission,
which can be represented as,
= − 3.20
where A21 is another Einstein coefficient. It can be shown that if the

population in the ground and excited states are the same, then
= 3.21
Equation 19 reveals that in induced emission, spontaneous emission

increases as the wave number increases. It also reveals that the
probabilities for stimulated absorption and emission are the same.
Therefore, transition that has a high induced absorption will also has a
high emission. The equation is very significant in laser design because
Laser operates entirely on induced emission.
Dipole moment is a very serious parameter that govern the selection rule
(i.e. allowed and forbidden transitions). For example, magnetic field can
interact with magnetic moment and cause transition seen in electron spin
spectroscopy and nuclear spin resonance spectroscopy, the oscillating
electric field can interact with electric charges (i.e. positive charges from
the nuclei and negative charge from electron cloud) and lead to
transition in UV, atomic absorption and fluorescence spectroscopy.
Another example is that for a molecule to be IR active, there must be a
change in dipole moment as it vibrates when IR absorption occurs.
72
Finally, spectroscopy requires transition between energy states and not

all transitions are possible. The change in dipole moment governs
allowed transition. Dipole moment is defined as the summation of the
product of charge and vector position for all charge particles. That is,
= ∑ 3.22
However, to evaluate the strength of interaction that cause transition, the

dipole moment is called the transition dipole. It is interesting to state
that absorption and emission cannot violates Pauli’s exclusion
principles, (which states that not more than two electrons can occupy a
given orbital) indicating that there is some restriction to those transition
that are possible or forbidden. The Einstein coefficients are related to the
wave function of the ground and excited states (i.e.  ∗
respectively) through the transition moment, R21, by considering the
quantum postulate relationship that link expectation in value of an
observable (in this case, the transition dipole moment) with the wave
functions. Therefore,
= ∫ ∗  3.23
The transition probability is given by the square of the transition

moment (R21) and is related to the Einstein coefficient according to the
following equation,
= | | 3.24
( )
The transition probability, | | is also related to spectroscopy

selection. Selection rules use the quantum numbers of the initial and
final states to predict allow or forbidden transition. If the states do not
satisfy the selection rules, then the electric-dipole transition rate will be
zero. Transitions that obey the electric-dipole selection rules are called
allowed transitions, while those which do not obey the rules are called
forbidden transitions. Electric dipole allowed transitions have high
transition probabilities and therefore have short radiative lifetimes,
typically in the range 1–100 ns. Forbidden transitions, by contrast, are
much slower. The different time-scales for allowed and forbidden
transitions lead to another general classification of the spontaneous
emission as fluorescence and phosphorescence, respectively.
Fluorescence is a process in which the photon is emitted within a few
nanoseconds after the atom has been excited, while phosphorescence
gives rise to ‘delayed’ emission which persists for a substantial time.
In conclusion, selection rule for transition occurring through interaction
with the electric vector of the radiation (i.e. electric dipole selection
rule) is define as forbidden when | | = 0 but allowed when | | is
non zero. It should be noted that non zero | | value can be found in
some transition where the ground and the excited states have zero dipole
73
CHM 307 MODULE 2
moment. For example, the transition from π to π* due to promotion of

electron in ethylene. The figure below shows (a) π molecular orbital of
ethylene (b) π* molecular orbital of ethylene
Fig. (a) π molecular orbital of ethylene (b) π* molecular orbital of

ethylene
Therefore, non zero value of the transition moment, R21 can be observed
in some molecules, even when the two states do not have permanent
dipole moment.
Since the transition moment is a function of the dipole moment, its

probabilities will also have components along the three coordinates.
Therefore, we have,
= ∑ , = ∑ and = ∑
21
Consequently, the R will also have components in the x, y and z
directions, which can be expressed as,
= ∫ ∗   , = ∫ ∗   and = ∫ ∗  
Consequently,
⌈ ⌉ = ( ) + + ( )
⌈ ⌉ = ∫ ∗   + ∫ ∗   + ∫ ∗  
3.25
Based on the number of interactions between radiation and light,

radiative transition can be classified into electric dipole, magnetic
dipole, electric quadrupole, magnetic quadrupole, electric octupole, etc.
Characteristics of each of these transitions are shown in the Table 3.1.
Data presented in Table 3.1 reveals that the rate of transition decreases
with increase in multipolarity (i.e. from dipole to quadrupole to
octupole). Also evident from the results is that magnetic interaction
becomes weaker by the same factor that the electric interaction
increases. Consequently, electric dipole is the strongest transition by
several order of magnitude indicating that other transitions are
negligible.
74
Table 3.1: Classification and characterization of radiative transition

based on multipolarity
Transition Einstein coefficient, Radiative life Parity

A (S-1) time (s) change
7 9
Electric dipole 10 – 10 1-100 ns Yes
3 5
Magnetic dipole 10 -10 0.01-1 ms No
3 5
Electric 10 -10 0.01-1 ms N0
quadrupole
Magnetic 0.1 -10 0.1-10 s Yes
quadrupole
Electric octupole 0.1-10 0.1-10 s yes
Worked example 1
Calculate (i) the dipole moment for HCl given the following data, =
(124.0,0,0), = (−3.5, 0, 0), = 2.70 × 10 =
2.70 × 10 . (ii) Do you expect the transition moment to be
equal to zero? Give reason for your answer.
Solution
The dipole moment in various directions are given as, = ∑ ,

= ∑ and = ∑ . The total dipole moment is the sum of
all the dipole moment from all direction. Therefore,
= [(2.70 × 10 )(124)
(
+ −2.70 × 10 )(−3.5)]
= (334.8 + 9.5) 10 = 343.95 × 10
= = [(2.70 × 10 )(0) + (−2.70 × 10 )(0)]
=0
= = (2.70 × 10 )(0) + (−2.70 × 10 )(0)
=0
(i) The total dipole moment is equal to
= + + = 343.95 × 10 +0+0
= 343.95 × 10
The transition moment is given as = ∫ ∗  . Since the value
of the dipole moment is non zero, then the integral will be non zero.
75
CHM 307 MODULE 2
Worked example 2
Given the following data for hydrogen atom, show that hydrogen
molecule cannot exhibit transition upon interaction with electromagnetic
radiation. . = (124.0,0,0), = 2.70 × 10
Solution
The dipole moment of hydrogen molecule can be calculated as follows,
= [(2.70 × 10 )(124)
+ (−2.70 × 10 )(124)] = 0
Since the dipole moment is zero, the transition moment is also zero,
hence there will be no transition when the molecule interacts with
electromagnetic radiation because the square of the transition dipole
moment is zero.
3.2 Vibrational spectroscopy
The development of Infra-red and Raman spectroscopy gave vibrational

spectroscopy a wider range of application for almost all types of
materials and in various physical states (gas, liquid and solid), especially
for covalently bonded compound.
The compression and extension of a chemical bond can be treated in

terms of the extension and compression of a spring, which obeys Hooke’
s law. According to Hooke’s law, the restoring force (FH) required to
restore the spring to its original position (i.e., the restoring force is given
by,
( )
= = − − =−
3.25
where k is the force constant (the magnitude of the force constant

determines the strength of the bond), V(x) is the potential energy and r is
the internuclear distant, − = The energy associated with this
extension is given by,
Rearrangement of equation 16 and integration gives the value for the

energy (i.e. potential energy (V(x) = E) as follows,
76
( ) = −
( ) = −
= − 3.26
Equation 17 shows that the restoring force is proportional to the

extension and that the energy is proportional to the square of the
displacement. A system of this nature corresponds to the simple
harmonic oscillator. Therefore, the model is known as a vibrating
diatomic molecule model or the simple harmonic oscillator model.
Although this model is an approximation, it forms the bases for
analysing the vibrational spectra of molecules.
3.2.1 The simple harmonic oscillator
A plot developed from equation 16 will displayed a pattern shown in

Fig. 3.2, that is a graph showing energy plotted against inter nuclear
distant. The zero of the curves appears when the condition, r = req is
fulfilled. Any energy in excess of the one obtained under this condition
will originate from extension or compression of the bond.
The quantum mechanical Hamiltonian for a one-dimension simple

harmonic oscillator is given as,
ħ
= + 3.27
where = and is called the reduced mass of the system.
Consequently, the Schrodinger equation for this system becomes,

= −  =0 3.28
ħ ħ
The solutions to the above equation are

= + ℎ 3.29
 = ( ) 3.30
!
where v is the vibrational quantum number, ( ) is called Hermite

/
polynomial and y is given as, = − and is the
classical vibration frequency given as,
= 3.31
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CHM 307 MODULE 2
Fig. 4.1: The Morse potential (blue) and harmonic oscillator potential
(green).
(Source: https://en.wikipedia.org/wiki/Morse_potential)
Equation 3.31 reveals that the oscillating frequency increases with k (i.e.
the stiffness of the bond but decreases with . The unit of the oscillation
frequency in equation 19b is in Hertz (Hz). To convert this frequency to
spectroscopic unit (i. e cms-1), equation 19c is divided by c, the speed of
light. This gives,
= 3.32
Also, the vibrational energy can be expressed in spectroscopic unit by
dividing equation 3.33 by hc and we have,
∈ = = + 3.33
Equations 3.32 and 3.33 are expressions for the only energy allowed for
simple harmonic oscillator. The vibrational quantum number (i.e. v)
takes values of v = 0,1,2……. Therefore, accordingly, the vibrational
quantum number is equally spaced by =ℎ . The lowest
vibrational energy can be obtained from these equations when v = 0.
The results are = ℎ (in Hz) or ∈ = (in cm-1). This
is the minimum energy a molecule may has, even at absolute zero
temperature and is a consequence of uncertainty principle. Hence a
78
diatomic molecule (and other molecules) can not possess vibrational

energy that is numerically equal to zero, indicating that the atoms can
never be completely at rest with respect to each other. The value of the
energy obtained under this condition is called zero-point vibrational
energy ( ℎ or ). The zero point vibrational energy is a
function of the classical vibrational frequency, the strength of the
chemical bond and on the atomic masses (Recall, = or
= ). The concept of the zero-point vibrational energy draws

a major line of distinction between classical mechanics and wave
mechanics. Classically, the energy of a molecule can assume any
integer values ranging from negative, zero and positive values. Quantum
mechanically, the energy of a molecule is restricted to only certain
permissible value. Therefore, wave mechanics insist that the vibrational
energy of any molecule must have at least the minimum energy (i.e. the
zero-point vibrational energy).
The selection rule for simple harmonic oscillator can be derived from
the Schrödinger equation and without prove it can be stated as, ∆ =
±1. This rule applies if the interaction of radiation with matter brings a
change in the dipole moment of the molecule, which is possible for
heteronuclear diatomic molecule. Homonuclear cannot be studied using
vibrational spectroscopy because they have no dipole moment. M
As stated before, emission involves transition from higher level to lower

level while absorption involves transition from lower level to higher
level). If the selection rule is applied to the simplest transition involving
emission (v+1 v) and absorption, (v v+1), the results of the
calculations are expressed in equation 20 and 21 for absorption and
emission respectively,
∈ → = ( + ) − ( +1+ ) = − =
− 3.34
∈ → = ( +1+ ) − ( + ) = − =
3.35
Equations 22 and 23 reveals that the amount of energy absorbed is equal

to the amount emitted. This is true for any value of v. Therefore, there
exist vibrational levels that are equally spaced because transition
between two neighbouring states give rise to the same energy change. It
is significant to state that the wave number of the spectral line absorbed
or emitted is equal to the energy change. i.e., = = .
Therefore, a molecule absorbs radiation only if it can coherently interact
79
CHM 307 MODULE 2
and it is only possible if it is the radiation of its own oscillating

frequency.
Worked example 3
HCl shows a very intense absorption at 2886 cm-1, a weak absorption at

5668 cm-1 and a weaker absorption at 8347 cm-1. Calculate the following
(i) The equilibrium frequency of absorption

(ii) The anharmonicity constant
(iii) The force constant ([Mass of H = 1.6727 amu, Mass of
chlorine = 35.435 amu)]
(iv) The classical vibrational energy of the molecule if v = 2
Solution: Three set of equations can be generated for the fundamental

absorption, first and second overtones as follows,
(1 − 2 ) = 2886 1
2 (1 − 3 ) = 5668 2
3 (1 − 4 ) = 8347 3
Expanding the brackets in equations 1, 2 and 3. We have equations 4, 5

and 6 respectively.
− 2 = 2886 4
2 − 6 = 5668 5
3 − 12 = 8347 6
(i) Equations 4, 5 and 6 can be solved simultaneously. This can be

achieved by multiplying equation 4 by 3. Equation 4 + equation 5
– equation 6, element the meddle terms (i.e. ) and we have,
= 2989.50 .
(II) The value of the anharmonicity constant, can be estimated by
substituting for in any of the equation. For example, for the
second first overtone, Xe = 0.01739
(III) The force constant can be solved by using the equation, =
.Making k the subject of the equation, we have, =
4 = 516 Nm-1.
(IV) The classical vibrational energy can be calculated using the
equation, ∈ = + , which gives 4484.25 cms-1
(for v = 2)
80
3.3 Rotational spectroscopy
As a first approximation, the rigid rotor model can be used to study

rotational motion of a molecule. Rigid rotor explains a rotation that
proceeds without changes in distance. The total energy of a rigid rotor
should consist of the sum of potential and kinetic energy. However,
since the distance is fixed, the energy can be assumed to be dominantly
kinetic, that is rotational energy and can be written as,
= ∑ 3.35
when mi and vi are the mass and the velocity of the rotating body. The
linear velocity is related to the angular velocity according to the
following equation,
=
Therefore, = × and the rotational energy can be expressed as,
= ∑ ( × ) 3.36
The angular velocity is a scaler quantity hence the above equation can
be simplified as follows,
= ( × )=
2 2
= ∑ = 3.37
where li is the angular momentum of ith particle while L is the angular

momentum of the entire system. If the moment of inertia is denoted as
I, then = . Therefore,
=
3.38
The above equation reveals that the energy of a rigid rotor increases
with increase in angular frequency and with moment of inertia.
From the above, it can be inferred that the classical energy of a particle
which rotates around an axis is given by E = ½ I2. where I is the
moment of inertia and  is the angular velocity in radian per second.
The moment of inertia, I is a function of mass of the particle (m) and the
radius of separation (r) and can be expressed as I = mr2.
The number of axis through which rotation can occur is infinite and so
the number of possible moments of inertia is also infinite. In order to
overcome this problem, we introduce a second-rank tensor quantity
(called the inertia tensor), which can be considered as an ellipsoid whose
width in any direction is a measure of the corresponding moments of
inertia.
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CHM 307 MODULE 2
The three principal axes of this ellipsoid are mutually perpendicular.

One of them relates to the maximum possible moment of inertia (IC),
one to the minimum possible moment of inertia (IA) and the other to the
intermediate possible moment of inertia (IB). Based on the relative
values of their three principal moments of inertia, molecules can be
classified into four major groups as presented in Table 1.
Table 1: Classification of molecules based on the relative values of

their principal moment of inertia
Types of molecule Property Examples

Spherical top IA = I B = I C CH4, CCl4 and SF6
Symmetric top IB = ICIA and IA 0
(a) Prolate: IB = IC> CH3I,
IA
(b) Oblate: IB = IC< BF3, C6H6
IA
Linear rotor IA = 0, IB = IC CO2, N2O, C2H2
Asymmetric top IA IB IC H2O, C2H3Cl
Considering the above information, the classical rotational energy of an

arbitrary object can be expressed as,
= + + 3.39
where A, B and C are the principal axes of rotation
3.3.1 Angular momentum
Angular momentum can be analysed using classical and quantum

mechanical approaches. Classically, angular momentum can take any
value but quantum mechanically, angular momentum is restricted to
certain permissible value, which is expressed in the equation 3.40,
= ( + 1) 3.40
where J is the rotational quantum number (which must be zero or

positive), h is the Planck constant. In molecular spectroscopy, our
concern is centered on possible changes in molecular energies and we
can develop equation for allowed value of the molecular energy through
classical approach. Classically, angular momentum is given as p = Ie
(where I is the moment of inertia) but the rotational energy is ½ I2.
Therefore,
= = 3.41
82
Substitution for p2 in equation 3.41 (using equation 3.40), yields

equation 3.42 and upon simplification, equation 33 is obtained.
( )
=
3.42
( )
=
3.43
In order to expressed the rotational energy in spectroscopic unit, we

divide both sides of equation 3.43 by hc (where c is the speed of light).
This gives
( )
∈ = = = ( + 1)
3.44
Equation 3.44 can be written as ∈ = ( + 1). = and is

called rotational constant expressed in cm-1. The selection rule for the
allowed transition is J = ±1. Let us consider the changes associated
with some transitions as follows,
(i) J = 0 to J =1
∆∈ = ∈ − ∈
=2 −0=2
(ii) J = 1 to J = 2
∆∈ = ∈ − ∈
= 2B(2+1) –B(1+1) = 4B
(iii) J = 2 to J = 3
∆∈ = ∈ − ∈
= 3B(3+1) –2B(2+1) = 6B
(iv) J = 3 to J = 4
∆∈ = ∈ − ∈
= 4B(4+1) –3B(3+1) = 8B
Generally, for a transition from J to J+1 state, the change in rotational

energy will be B(J+1)(J+2) – BJ(J+1) = (BJ2 + 3BJ + 2B) – (BJ2 - B) =
2B(J+1). Therefore, rotational transition will be characterised by a
stepwise raising of the rotational energy by a multiple of 2. This can be
seen in Fig. 3.3. The diagram reveals that only J to J+1 transition is
allowed. This is consistent with the selection rule, which give allowed
transition to be J = ±1. The implication is that for absorption, the
transition is from J to J+1 but for emission, spectral will only be
produced when the transition is from J+1 to J. In both cases, the spacing
between each spectral transition is 2B.
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CHM 307 MODULE 2
J
5
2B 4B 6B 8B 10B 12B 14B 16B
Fig. 3.3: Diagram showing allowed rotational transition
3.3.2 Centrifugal distortion: the semi-rigid body
A rotating molecule is not perfectly rigid. This means as the speed of

rotation increases, the bond stretches (analogous to a case of swinging a
weight attached to elastic in a circle) and leads to centrifugal distortion.
This implies that equation 34 cannot be accurate in explaining the
rotational energy of a real molecule. Therefore, we introduce a
centrifugal distortion term to account for the rotation behaviour of a real
molecule. Equation 34 is hereby amended to equations 35 (in Joules)
and 33 (in spectroscopic unit, cm-1),
= ( + 1) − ( + 1)
3.45
∈ = = ( + 1) − ( + 1)
3.46
Introducing rotation constants, B = and D = we have the

following equation
∈ = ( + 1) − ( + 1) 3.47
84
Considering the rotational transition from level J to level J+1, in the

presence of centrifugal distortion, we can calculate the allowed change
in energy as follows,
∆∈ = ∈ −∈
= ( + 1)( + 2)] − ( + 1) ( + 2) − ( + 1) − ( + 1)
= ( + 1)( + 2)] − ( + 1) − ( + 1) ( + 2) − ( + 1)
= ( + 3 +2− − − ) ( )
+1 ( + 4 +4− )
= (2 + 2) − ( + 1) (4 + 4)
= 2 ( + 1) − 4 ( + 1)
Again if we ignore the centrifugal distortion, the change in rotational

energy becomes 2B(J +1) as before. Therefore, lines on pure rotational
spectrum is often equally spaced by 2B. However, if there is centrifugal
distortion, the effective rotation constant B will depend on J and the
lines will not be equally spaced but will occurs at positions defined by
the equation, 2 ( + 1) − 4 ( + 1) . The centrifugal distortion
constant, D and frequency of oscillation are related according to
equation 3.48,
= =

3.48
The force constant itself, = 4 . Equations 3.42 to 3.44 apply

to simple harmonic force field. The appropriate equation for the
anharmonic force field will have more correction terms as expressed in
equation 3.49,
∈ = ( + 1) − ( + 1) + ( + 1) + ( + 1)
3.49
Worked example 4
(a) What is the differences and similarity between absorption and

emission. Hence use the selection rule with respect to the
simplest harmonic transition to show that the amount of energy
associated with absorption is the same with that associated with
emission.
(b) With suitable equation, give reason to show that wave number of
the spectral line absorbed or emitted is equal to the energy
change.
(c) Under what condition can a radiation absorbed by a molecule be
effective?
(d) Use the time independent spectroscopic theory to explain the
likelihood of an absorption to lead to transition. What is the
relationship between this theory and the Schrödinger equation?
(e) Write an expression that defines molecular transition moment.
Hence what are the factors that influence.
85
CHM 307 MODULE 2
(f) Use the matrix element associated with the time independent
spectroscopy theory to explain forbidden transition and transition
selection rule (i. e allowed transition).
Solution
(a) Emission involves transition from higher level to lower level while
absorption involves transition from lower level to higher level). If the
selection rules is applied to the simplest transition involving emission
(v+1 v) and absorption, (v v+1), the results of the calculations are
expressed in equations1 and 2 for absorption and emission respectively,
∈ → = ( + ) − ( +1+ ) = − =
− 1
∈ → = ( +1+ ) − ( + ) = − =
2
Equations 1 and 2 reveal that the amount of energy absorbed is equal to

the amount emitted. This is true for any value of v.
(b) Therefore, there exist vibrational levels that are equally spaced
because transition between two neighbouring states give rise to the same
energy change. Therefore, the wave number of the spectral line absorbed
or emitted is equal to the energy change. i.e, = = .
(c) A molecule absorbs radiation only if it can coherently interact

and it is only possible if it is the radiation of its own oscillating
frequency.
(d) According to the time-dependent spectroscopic theory, the

probability of a molecule to absorb a light photon is given by the
following expression, ← ⌈⟨ | |0⟩⌉ . where [⟨ | |0⟩] is the
matriz element of transition dipole moment. This factor is related to the
Schrödinger wave equation according to the following equation,
⟨ | |0⟩ = ∫ ∗ where and ∗ are the molecular wave
functions of the initial and excited states respectively.
(e) The total dipole moment is a vector which can be expressed as, μ =
∑ where qi is the charge of the ith particle and is the radius
vector of the ith particle. The summation is done such that all particles
are considered. From the time-dependent spectroscopic theory, it can be
seen that the rate of transition is proportional to,
86
i. and hence the intensity of the incident light

ii. The square of the Z-component of the dipole moment matrix
The time independent spectroscopy equation also reveals that the matrix
element,⟨ | |0⟩ depends on the symmetry of both the initial and
excited molecular states, which in turn depends on the quantum number
(vibrational or rotational quantum numbers, as the case maybe).
(f) Those quantum numbers that gives the matrix element (⟨ | |0⟩)
a value of zero, presents molecular transition that is called forbidden
transition. On the other hand, those transitions that results from quantum
numbers that gives non zero values lead to transition selection rules,
which signifies allowed transition.
Worked example 5
(a) What is the requirement for the production of pure rotational

spectrum by a molecule. Hence emulate the different selection
rules that are applicable to the production of pure rotational
spectrum?
(b) Under symmetry conditions, what are the point groups that are
associated with the production of pure rotational spectra
Solution.
(a) The basic requirement for the production of pure rotational

spectra is that there should be an oscillating dipole associated
with molecular rotation. This implies that the molecule must have
a permanent dipole moment indicating that the dipole moment
must not be equal to zero, i.e µ 0. This is the gross selection rule
for micro wave and for pure rotational spectroscopy. The other
selection rule arises from allowed changes in angular momentum
and is called the specific selection rule. This is given as J =  1.
(b) The only set of molecules that can have permanent dipole
moment are molecules of the point group CnV or Cn. Hence these
molecules have rotational spectra.
Worked example 6
What is the formula for calculating the translational energy of a

molecule? Hence why is the energy often considered as insignificant in
molecular spectroscopy?
87
CHM 307 MODULE 2
Solution
The translational energy of a molecule is similar to the energy of a

particle in a three-dimensional box. This can be expressed as,
ℎ
( , , ) = + +
2
In general, the separation of the translational energy levels is many

orders of magnitude smaller than the Boltzmann factor, kT,even for a
box with dimensions on the order of molecular sizes. Therefore,
translational behaviour of molecules is often treated under classical
mechanics and not quantum mechanics, which is vital in molecular
spectroscopy.
Worked example 7
(a) Derive an expression for the classical and quantum rotational

energy of a spherical top molecule
Solution
For a spherical top molecule, I = IA = IB = IC. This means that the three
principal axes of rotation are equal. The classical energy is given by,
1 1 1
= + +
2 2 2
Since IA = IB = IC = I, the above equation becomes
= ( + + ).
But = . = . Therefore, = = . Since P is
quantized and = ( + 1). Then the allowed rotational energy
for the spherical top molecule is = . ( + 1) = ( + 1)
3.4 Rovibrational spectroscopy
As stated before, in molecular spectroscopy, the total energy of a

molecule is the sum of contributions from electronic, vibrational and
rotational energies. However, if we ignore the electronic energy (which
is possible when we use electromagnetic frequency of low energy), then
the total energy will be the sum of vibrational and rotational energy and
can be expressed as follow,
( , ) = + − + + ( + 1) + ( + 1)
3.50
The absorption of energy equivalent to E(V,J) will lead to a transition.
The absorbed energy that will initiate such a transition will correspond
88
to the infra-red spectroscopy. The gross selection rule for this transition
is that a molecule must have a dipole moment that changes as it is
vibrating. Mathematically, dµ/dt  0. The specific selection rules for real
vibration is v = 1, 2 and 3. In most cases, a change in the
vibrational quantum number will be accompanied by a change in the
rotational quantum number, J, under the selection rule, J = 0, 1. The
study of a system of this nature that is characterised by both vibrational
and rotational changes is called vibrotational or rovibrational
spectroscopy. Vibrotational transitions often leads to the production of
vibrotational bands, consisting of P, Q and R bands.
3.5 Electronic spectroscopy
According to the Born-Oppenheimer approximation, the energy of a

molecule can be considered to be the sum of vibrational, rotational and
electronic energies. Hence,
= + +
3.51
This implies that the change in energy can be expressed as,
∆ = ∆ + ∆ + ∆
3.52
For rotational spectra to occur, the molecule must have a permanent

dipole, vibrational spectra occurs when the dipole of the molecule
changes during vibration. However, electronic spectra can be produced
for all molecules because changes in the distribution of electrons in a
molecule is always associated by a change in the dipole moment of the
molecule. This gives electronic spectroscopy, an edge over vibrational
or rotational spectroscopy. For example, homo nuclear molecules such
as H2, N2 and O2 do not show rotation or vibration spectra but they do
show electronic spectrum, from which vibration and rotation parameters
can be obtained. Extension of equation 48 gives equation 3.53 for
anharmonic and rigid rotor.
= + + − + + ( + 1) +
( + 1) 3.53
If we ignore the contribution from molecular rotation, equation 50
changes to equation 3.54,
= + + − +
3.54
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CHM 307 MODULE 2
Self Assessment Exercise
1. Given that N1 represent the population of the first level, i.e. level
1 and A12 is the Einstein coefficient of spontaneous emission,
show that N1 has an exponential relationship with A12
2. State at least one example of spectroscopic techniques that
employs transition in vibrational, rotational and Electronic
transition.
3. (a) What is selection rule in spectroscopy. Hence present an
equation that gives the probability of spectroscopic
transition
(b) What is the relationship between the wave function and
the probability stated above ?
(c) What are the factors that affects the rate of transition and
the magnitude of the matrix element
(d) What is the relationship between the value of transition
matrix element and probability of transition
4. (a) Define what is dipole moment and transition dipole
moment
(b) What is the relationship between the wave function and
transition dipole moment?
(c) What is the relationship between transition dipole moment
and the transition probability?
5. Based on electric dipole moment, differentiate between
allowed and forbidden transition
6. Explain why ethylene exhibit non zero transition
probability even if it does not have a permanent dipole
moment.
7. The selection rule for the allowed transition is J = ±1.
Calculate the changes expected when the following
transition occurs, (i) J= 0 to J =1, (ii) J = 1 to J = 2,
(iii) J = 2 to J = 4 (iv) J =3 to J = 4
8. What are the shortcoming of rotational and vibrational
spectroscopy over electronic spectroscopy
Answers to Self Assessment Exercise
1. Applying the Einstein theory of spontaneous radiation, decay

of excited state E1 it can be stated that
= − . 1
Re-arranging and integrating equation 1, we have equation 3.10 and
3.11 respectively,
( )
∫ = −∫ 2
( )
90
( )
ln = − 3
( )
( ) = ( ) 4
2. Transition between the vibrational energy levels is achieved by

infra-red radiation, transition between rotational energy levels is
achieved by far infra-red and by micro wave radiations while
electronic energy levels transition is achieved by using visible
light and ultra violet red radiations
3. The selection rule is a mathematical expression that can be used
to know allowed or forbidden spectroscopic transition.
According to the time-dependent spectroscopic theory, the
probability of a molecule to absorb a light photon is given by the
following expression,
← ⌈⟨ | |0⟩⌉
where | |0⟩ is the matriz element of transition dipole moment. This
⟨
factor is related to the
(b) Schrödinger wave equation according to the following equation,

⟨ | |0⟩` = ∫ ∗ 1
∗
where and are the molecular wave functions of the initial and
excited states respectively. The total dipole moment is a vector which
can be expressed as,
μ = ∑ 2
where qi is the charge of the ith particle and is the radius vector of the
ith particle. The summation is done such that all particles are considered.
(c) From equations 1 and 2, it can be seen that the rate of transition is
proportional to,
iii. and hence the intensity of the incident light

iv. The square of the Z-component of the dipole moment matrix
Equation 1 also reveals that the matrix element, ⟨ | |0⟩ depends on

the symmetry of both the initial and excited molecular states, which in
turn depends on the quantum number (vibrational or rotational quantum
numbers, as the case maybe).
(d) Those quantum numbers that gives the matrix element a value of
zero, presents molecular transition that is called forbidden
transition. On the other hand, those transitions that results from
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CHM 307 MODULE 2
quantum numbers that gives non zero values lead to allowed transition
and hence transition selection rules.
4. (a) Dipole moment is defined as the summation of the product

of charge and vector position for all charge particles. That is,
= ∑
However, to evaluate the strength of interaction that cause transition, the

dipole moment is called the transition dipole.
(b) The Einstein coefficients are related to the wave function of the
ground and excited states (i.e  ∗ respectively) through
the transition moment, R21. This can be derived by considering
the quantum postulate relationship that link expectation in value
of an observable (in this case, the transition dipole moment) with
the wave functions. Therefore,
= ∫ ∗ 
(c) The transition probability is given by the square of the transition

moment (R21) and is related to the Einstein coefficient according
to the following equation,
= | |
( )
5. Transitions that obey the electric-dipole selection rules are called

allowed transitions, while those which do not obey the rules are
called forbidden transitions. Electric dipole allowed transitions
have high transition probabilities and therefore have short
radiative lifetimes, typically in the range 1–100 ns. Forbidden
transitions, by contrast, are much slower. Selection rule for
transition occurring through interaction with the electric vector of
the radiation (i.e electric dipole selection rule) is define as
forbidden when | | = 0 but allowed when | | is non zero.
6. It should be noted that non zero | | value can be found in

some transition where the ground and the excited states
have zero dipole moment. For example, the transition from π
to π* due to promotion of electron in ethylene. The figure
below shows (a) π molecular orbital of ethylene (b) π* molecular
orbital of ethylene
92
Fig. (a) π molecular orbital of ethylene (b) π* molecular orbital of

ethylene
Therefore, non zero value of the transition moment, R21 can be observed
in some molecules, even when the two states do not have permanent
dipole moment.
7. The selection rule for the allowed transition is J = ±1. The

changes associated with some transitions as follows,
(v) J = 0 to J =1
∆∈ = ∈ − ∈
=2 −0=2
(vi) J = 1 to J = 2
∆∈ = ∈ − ∈
= 2B(2+1) –B(1+1) = 4B
(vii) J = 2 to J = 3
∆∈ = ∈ − ∈
= 3B(3+1) –2B(2+1) = 6B
(viii) J = 3 to J = 4
∆∈ = ∈ − ∈
= 4B(4+1) –3B(3+1) = 8B
Generally, for a transition from J to J+1 state, the change in rotational

energy will be B(J+1)(J+2) – BJ(J+1) = (BJ2 + 3BJ + 2B) – (BJ2 - B) =
2B(J+1). Therefore, rotational transition will be characterised by a
stepwise raising of the rotational energy by a multiple of 2.
1. For rotational spectra to occur, the molecule must have a

permanent dipole, vibrational spectra occur when the dipole of
the molecule changes during vibration. However, electronic
spectra can be produced for all molecules because changes in the
distribution of electrons in a molecule is always associated by a
change in the dipole moment of the molecule. This gives
electronic spectroscopy, an edge over vibrational or rotational
spectroscopy.
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CHM 307 MODULE 2
4.0 CONCLUSION
Spectroscopy deals with the study of interaction of radiation with matter.

When radiation in form of photon strikes matter, several processes may
be observed including, absorption, emission, molecular motions
(vibration, rotation, electronic motions, etc).
5.0 SUMMARY
In order to obtained a spectrum that can give quality information, the

interaction of radiation with matter must lead to appropriate selection
rules. They are three fundamental types of spectroscopy namely,
vibrational spectroscopy (liken to simple harmonic oscillator and
adjustment to anharminicity to suite real molecules), rotational
spectroscopy (liken to Hook’s law model and consequent amendment
with rigid rotor model and centrifugal distortion) and electronic
spectroscopy, which can be applied virtually to all types of matter.

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Struve, W. S. (1987). Fundamental of molecular spectroscopy Springer



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CHM 307 MODULE 2
UNIT 2 COUPLING IN SPECTROSCOPY
CONTENT
1.0 Introduction
2.0 Intended Learning Outcomes
3.0 Main Content
3.1 Spin orbit coupling
3.1.1 Fine structure
3.1.2 Multiplicity
3.2 Russell-Saunders coupling
4.3 jj coupling
4.0 (i) Self Assessment Exercises and Answers
(ii) Class Activity
5.0 Conclusion
6.0 Summary
1.0 INTRODUCTION
Observation of two bands of silver atoms Stern and Gerlach created

disagreement with one of the principles of quantum mechanics because
an angular momentum l is expected to give rise to 2l + 1 orientations
and can only be equal to 2 (i.e two bands) if l= ½. This contradict the
expectation that I must be an integer. This led to the findings that the
observed angular momentum was not due to orbital angular momentum
(the motion of an electron around the atomic nucleus) but from the
motion of the electron about its own axis. This intrinsic angular
momentum of electron, arising from its motion about its axis is called
spin. Dirac further investigated spin angular momentum by combining
quantum mechanics with special relativity and established the theory of
relativistic quantum mechanics. Consequently, it was concluded that the
spin of an electron about its own axis does not necessarily satisfy the
same boundary conditions as those for a particle circulating around a
central point, indicating that the quantum number for spin angular
momentum is subject to different restrictions. In order to distinguish the
spin angular momentum from orbital angular momentum, the spin
quantum number s (in place of l and like l, s is a non-negative number)
and ms, the spin magnetic quantum number, for the projection on the z-
axis. The magnitude of the spin angular momentum is { ( + 1)} ћ. The
components, ћ is restricted to the 2s+1 value with = , − 1, … −
.
Spin is an intrinsic property and for electron, only one value of s is

allowed (i.e s = ½ ). Consequently, the magnitude of the spin angular
96
momentum for electron is, +1 = ћ. This gives 0.8660ћ

as the spin angular momentum. This means that the magnitude of the
intrinsic spin angular momentum for an electron is 0.8660ћ and is
constant for all electrons. Consequently, the spin may lie in 2s+1 = 2(½)
+1 = 2 different orientation. One orientation correspond to ms = +½ (
usually represented as α or ↑) and the other is – ½ corresponding to β or
↓. This does not violate Pauli’s exclusion principle (which requires not
more than two electrons to occupied a given orbital) and Aufbau
principle which requires that the spin of electron must be opposed when
two electrons occupy a given orbital. Proton and neutron also have s =
1/2 , indicating that their spin angular momentum will be 0.8660ћ. The
difference between these elementary particles is that because their
masses is much heavier than electron, they will move at much slower
rate than electron.
Some other particle (such as mesons) have spin value of 1 (i.e s = 1)

indicating that their spin angular momentum would be {1(2 + 1)} ћ =
1.4142ћ. Photon is a spin-1 particle. It has zero rest mass, zero charge,
energy (given as hv), linear momentum (given as h/ λ or hv/c), an
intrinsic angular momentum of 1.4142ћ and travel at the speed of light
(i.e c).
Particles with half integer spin are called fermions while particles with
integer spin are called bosons. Therefore, electrons and protons are
fermions while photon is boson. It is worth stating that elementary
particles that bind fermions together are bosons indicating that matter
consist of assemblage of fermions held together by forces controlled by
bosons.
Table 4.1 shows various quantum numbers, values and other properties.
In the Table, the use of quantum numbers l and ml points toward orbital
angular momentum (circulation in space). s and ms denote spin angular
momentum (intrinsic angular momentum) while j and mj are for a
combination of orbital and spin momenta.
For many electron systems, upper case letters are used (i.e L, S, MS, ML,
J, MJ, etc). Clebsh-Gordon series is used to combine two angular
momenta. This is expressed as
= + , + − 2, … … . . [ − ]
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CHM 307 MODULE 2
2.0 INTENDED LEARNING OUTCOMES
i. Understand what is spin and the major contributors to spin

ii. Differentiate between orbital and spin angular momenta
iii. Identify the various quantum numbers related to angular
momentum
iv. Know what is coupling, spin-orbit coupling Russell-Saunders
coupling and jj- coupling and when they are most useful
v. Solve mathematical problems associated with spin and coupling.
3.0 MAIN CONTENT
3.1 Spin Orbit Coupling
There are two contribution to angular momentum of an electron. One is

a consequence of a magnetic moment that arises from its spin. The other
contributor exists because an electron with orbital angular momentum
(that is, an electron in an orbital with l > 0) behaves as a circulating
current, and possesses a magnetic moment that arises from its orbital
momentum. The interaction of the spin magnetic moment with the
magnetic field arising from the orbital angular momentum is called
spin–orbit coupling. The strength of the coupling, and its effect on the
energy levels of the atom, depend on the relative orientations of the spin
and orbital magnetic moments, hence on the relative orientations of the
two angular momenta. The dependence of the spin–orbit interaction on
the relative orientation of the spin and orbital momenta depends on the
total angular momentum of the electron, the vector sum of its spin and
orbital momenta. Consequently, when the spin and orbital angular
momenta are nearly parallel, the total angular momentum is high but
low when the two angular momenta are opposed.
Table 4.1: Properties of the angular momentum of electron
Quantum number Symbol Values Specification

Orbital angular l 0, 1, 2,….. { ( + 1)} ћ is the
momentum magnitude
Magnetic ml l, l-1,……-l Component on z axis =
ћ
Spin s ½ { ( + 1)} ћ is the
magnitude
Spin magnetic 1 { ( + 1)} ћ
± is the
2 magnitude
Total angular j l +s, l+s- { ( + 1)} ћ is the
momentum 1,..-j
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magnitude
Total magnetic Component on z axis =
ћ
The total angular momentum of an electron is described by the quantum

numbers j and mj, with j = l + (when the two angular momenta are in
the same direction) or j = l − (when they are opposed). The different
values of j that can arise for a given value of l account for the levels of a
term. For l = 0, the only permitted value is = − ( (the total angular
momentum is the same as the spin angular momentum because there is
no other source of angular momentum in the atom). When l =1, j may be
either (the spin and orbital angular momenta are in the same sense) or
(the spin and angular momenta are in opposite senses).
The dependence of the spin–orbit interaction on the value of j is

expressed in terms of the spin–orbit coupling constant, ̅ (expressed as a
wavenumber). For a given set of quantum numbers, s, l and j, the energy
of the level can be expressed according to equation 4.1
, = ℎ ̅ { ( + 1) − ( + 1) − ( + 1)} 4.1
For example, the unpaired electron in the ground state of sodium atom
has l = 0, so j = . Because the orbital angular momentum is zero in this
state, the spin–orbit coupling energy is zero (as is confirmed by setting j
= s and l = 0). When the electron is excited to an orbital with l = 1, it has
orbital angular momentum and can give rise to a magnetic field that
interacts with its spin. Under this configuration, the electron can have j=
or j = , and the energies of these levels are
1 3 5 1 3 1
, = ℎ ̅ × −1×2− × = ℎ ̅
2 2 2 2 2 2
1 1 5 1 3
, = ℎ ̅ × − 1 × 2 − × = −ℎ ̅
2 2 2 2 2
Another factor that affects the strength of spin-orbit coupling is the

nuclear charge. The greater the nuclear charge, the greater the
circulating current, and therefore the stronger the magnetic field. Since
the spin magnetic moment of the electron interacts with this orbital
magnetic field, the greater the nuclear charge, the stronger the spin –orbit
interaction. It has been found that the coupling increases sharply with
atomic number (as from Z=4). Whereas it is relatively small in H
(giving rise to shifts of energy levels of no more than about 0.4 cm−1), in
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CHM 307 MODULE 2
heavy atoms like Pb it is very large (giving shifts of the order of

thousands of reciprocal centimetres).
3.1.1 Fine structure
Fine structure is the structure in a spectrum due to spin-orbit coupling.

For example, two spectral lines are observed when the p electron of an
electronically excited alkali metal atom undergoes a transition and falls
into a lower s orbital. One line is due to a transition starting in a j =
level and the other line is due to a transition starting in the j = level of
the same configuration. The two lines are an example of the fine
structure of a spectrum (the structure in a spectrum due to spin–orbit
coupling). Fine structure can be clearly seen in the emission spectrum
from sodium vapour excited by an electric discharge (for example, in
one kind of street lighting). The yellow line at 589 nm (close to 17000
cm−1) is actually a doublet composed of one line at 589.76 nm (16956.2
cm−1) and another at 589.16 nm (16973.4 cm−1); the components of this
doublet are the ‘D lines’ of the spectrum. Therefore, in Na, the spin–
orbit coupling affects the energies by about 17 cm−1.
The total orbital angular momentum When several electrons are present,
it is necessary to consider how their individual orbital angular momenta
add together or oppose each other. The total orbital angular momentum
quantum number, L, tells us the magnitude of the angular momentum
through { ( + 1)} ћ. The number of orientation is 2L + 1, which is
distinguished by the quantum number ML. ML can take the following
values; L, L−1, . . . , −L. Similar remarks apply to the total spin
quantum number, S, and the quantum number MS, and the total angular
momentum quantum number, J, and the quantum number MJ. The value
of L (a non-negative integer) is obtained by coupling the individual
orbital angular momenta by using the Clebsch–Gordan series, which can
be written as,
= + , + − 1, … … . . | − |
The maximum value of = + is observed when the two orbital
momentum are in the same direction while the minimum value ( =
− ) is observed when they are in opposite direction. =
| − | is an intermediate value and signified intermediate between
the two.
Worked example 1
(i) Calculate the value of L for 2p electrons

(ii) What are the letters designated to L = 1, 2, 3,4 5 and 6?
(iii) state the orbital terms the 2p electrons can give rise to.
100
(iv) Why does a closed shell have zero angular momentum?
Solution
i. For 20 electrons, L1 = L2 = 1 hence the maximum value is

= + = 1 + 1 = 2, the intermediate value is = −
− 1 = 1 + 1 − 1 = 1 while the minimum is | − | =
|1 − 1| = 0. Therefore, for 2p electrons, L = 2, 1, 0
ii. When L = 1, 2, 3, 4, 5 and 6, they are designated the letters S,
P, D, F, G, H and I respectively.
iii. A p2 configuration can give rise to D, P, and S terms. The
terms differ in energy on account of the different spatial
distribution of the electrons and the consequent differences in
repulsion between them
iv. A closed shell has zero orbital angular momentum because all
the individual orbital angular momenta sum to zero.
3.1.2 The multiplicity
When there are several electrons to be taken into account, we must

assess their total spin angular momentum quantum number, S (a non-
negative integer or half integer) using Clebsh-Gordon series given as,
= + , + − 1, … … . . | − |
Electron has s = ½ which gives S = 1, 0 for two electrons (i.e s1 = s2 =
½).
3.2 Russell–Saunders coupling scheme
The quantum number j provides information of the relative orientation

of a spin of a single electron. However, when there are many electrons, J
provides similar information. The presence of several electrons outside a
closed shell (note, a closed shall has zero spin) requires consideration of
the coupling of all the spins and all the orbital momenta. Problem
arising from this, maybe complicated but can be simplified when the
spin-orbit coupling is weak (mostly for atoms of low atomic number).
The simplification is achieved by using the Russel-Saunders coupling
scheme. The scheme is based on the observation that, if spin–orbit
coupling is weak, then it is effective only when all the orbital momenta
are operating cooperatively. Consequently, the coupling assumes that all
the orbital angular momenta of the electrons couple to give a total L, and
that all the spins are similarly coupled to give a total S. Hence the two
momenta couples through the spin–orbit interaction to give a total J. The
permitted values of J are given by the Clebsch–Gordan series, which can
be written as,
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CHM 307 MODULE 2
= + , + − 1, | − |
3.3 J-J coupling
Russell–Saunders coupling fails when the spin–orbit coupling is large

(in heavy atoms, those with high Z). In order to overcome this
shortcoming, the individual spin and orbital momenta of the electrons
are coupled into individual j values; then these momenta are combined
into a grand total, J. This scheme is called jj-coupling. If the spin and the
orbital angular momentum of each electron are coupled together
strongly, it is best to consider each electron as a particle with angular
momentum j= or . These individual total momenta then couple as
follows:
3 and 3 J = 3, 2, 1, 0
= =
2 2
3 and 1 J = 2, 1
= =
2 2
1 and 3 J = 2,1
= =
2 2
1 and 1 J = 1, 0
= =
2 2
(i) Self Assessment Exercises
1. When electron in sodium is excited to an orbital with l = 1, it has

orbital angular momentum and can give rise to a magnetic field
that interacts with its spin. Calculate the energies of the level,
electron can have in terms of associated constant.
2. (i) Explain how observation of two bands in the spectrum of
silver atoms disagrees with quantum mechanics and give reasons
for the observation
(ii) Define the term, spin
3. Calculate the magnitude of spin for the following particles (i)
electron (ii) proton and neutron (iii) photon. How many
orientations can the spin lies?
4. In a single sentence, define what is spin orbit coupling. State two
factors that influences the strength of spin orbit coupling,
5. Use Clebsh-Gordon series to calculate the total spin of electron
6. What is the better coupling method, that is more effective when
the spin orbit coupling is weak? Hence define the preferred
coupling rule.
7. Under what condition will the Russel-Saunders coupling fails?
Hence what is best coupling method when it fails?
102
Answer to Self Assessment Exercise
1. Under the stated configuration, the electron can have j= or j = ,

and the energies of these levels are
1 3 5 1 3 1
, = ℎ
̅ × −1×2− × = ℎ ̅
2 2 2 2 2 2
1 1 5 1 3
, = ℎ
̅ × − 1 × 2 − × = −ℎ ̅
2 2 2 2 2
2. (i) Observation of two bands of silver atoms Stern and
Gerlach created disagreement with one of the principles of
quantum mechanics because an angular momentum l is expected
to give rise to 2l + 1 orientations and can only be equal to 2 (i.e
two bands) if l= ½. This contradict the expectation that I must be
an integer. This lead to the findings that the observed angular
momentum was not due to orbital angular momentum (the motion
of an electron around the atomic nucleus) but from the motion of
the electron about its own axis.
(ii) This intrinsic angular momentum of electron, arising from its
motion about its axis is called spin
3 The magnitude of the spin angular momentum is { ( + 1)} ћ.
(i) For electron, only one value of s is allowed (i.e s = ½ ).
Consequently, the magnitude of the spin angular momentum
for electron is, +1 = ћ. This gives 0.8660ћ as

the spin angular momentum. Consequently, the spin may lie
in 2s+1 = 2(½) +1 = 2 different orientation
(ii) For proton and neutron, allowed value of s is also 1/2.
Therefore, the magnitude of the spin angular momentum for
electron is, +1 = ћ. This gives 0.8660ћ as the

spin angular momentum. Consequently, the spin may also lie
in 2s+1 = 2(½) +1 = 2 different orientation
(iii) have spin value of 1 (i.e s = 1) indicating that their spin
angular momentum would be {1(2 + 1)} ћ = 1.4142ћ.
Consequently, the spin may lie in 2s+1 = 2(1)+1 = 3
orientations.
4. The interaction of the spin magnetic moment with the magnetic
field arising from the orbital angular momentum is called
spin–orbit coupling. The strength of the coupling, and its
effect on the energy levels of the atom, depend on
(i) the relative orientations of the spin and orbital magnetic
moments, hence on the relative orientations of the two angular
momenta
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CHM 307 MODULE 2
(ii) The nuclear charge also influences spin orbit coupling. The
greater the nuclear charge, the greater the circulating charges and
the magnetic moment, hence the strength of the spin-orbit
coupling.
5. When there are several electrons to be taken into account, we
must assess their total spin angular momentum quantum number,
S (a non-negative integer or half integer) using Clebsh-Gordon
series given as,
= + , + − 1, … … . . | − |
Electron has s = ½ which gives, = + , + − 1, … … . . − and
S = 1, 0 for two electron (i.e s1 = s2 = ½).
6. when the spin-orbit coupling is weak (mostly for atoms of low
atomic number). The simplification is achieved by using the
Russel-Saunders coupling scheme. The scheme is based on the
observation that, if spin–orbit coupling is weak, then it is
effective only when all the orbital momenta are operating
cooperatively.
7. Russell–Saunders coupling fails when the spin–orbit coupling is
large (in heavy atoms, those with high Z). In order to overcome
this shortcoming, the individual spin and orbital momenta of the
electrons are coupled into individual j values; then these
momenta are combined into a grand total, J.
4.0 CONCLUSION
Electron can move around the nucleus and around its own axis. Hence
electron has two set of angular momenta originating from orbital and
spin. They are orbital angular momentum and spin angular momentum.
Therefore, the total angular momentum is the sum of contribution from
spin and orbital.
5.0 SUMMARY
The interaction of the spin magnetic moment with the magnetic field
arising from the orbital angular momentum is called spin–orbit coupling.
The strength of spin-spin coupling depends on the nuclear charge, level
of orientation of spin moment and orbital magnetic moment. When the
spin-spin coupling is weak, the prefer coupling is Russell-Saunders
Coupling. However when the spin-spin coupling is high, Russell-
Sauders coupling fail given gap for jj-coupling as the preferred coupling.
104
1. What are the conditions requires for applicability and failures of

the following coupling
(1) J-J coupling (5 minutes)
(2) Russell-Saunders (5 minutes)

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106
MODULE 3
UNIT 1 GROUP THEORY AND SYMMETRY
CONTENT
1.0 Introduction
2.0 Intended Learning Outcomes
3.0 Main Content
3.1 Symmetry Operation
3.1.1 Identity operation
3.1.2 Proper rotation
3.1.3 Reflection operation
3.1.4 Improper rotation
3.1.5 Inversion operation
3.2 Symmetry Point Group
3.2.1 Classification of symmetric point group
3.3 Applications of symmetry
4.0 (i) Self-Assessment Exercise and Answers
(ii) Class Activity
5.0 Conclusion
6.0 Summary
7.0 References/Further Reading
1.0 INTRODUCTION
A system is said to have symmetry if it has a mirror image, indicating

that it will look the same if viewed in a mirror. The study of symmetry is
essential in chemistry because through the mathematical framework
known as group theory, it provides information that can be used to gain
insight into some physical and chemical properties of a system. Group
theory arises from classification of symmetry of molecule and it is a
useful tool that can provide information on the following,
i. Prediction of chirarity or polarity of a molecule

ii. Examination of chemical bonding and visualization of molecular
orbitals
iii. Prediction of the ability of a molecule to absorb light of a given
polarization and the associated spectroscopic transition
iv. Investigation of vibrational motion of a molecule
In symmetry, operation is an action that render an object or a molecule

indistinguishable (i.e. looking the same) after the action has been
performed. For example, if we rotate water molecule at 180  about the
axis that passes through the oxygen atom, it will look the same as the
water molecule before the rotation was performed.
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CHM 307 MODULE 3
Fig. 5.1: Symmetry operation: Rotation of water at 180 
Apart from rotation, there are different types of symmetry operations.

However, each symmetry operation has a corresponding symmetry
element, which is the axis, plane, line or point through which symmetry
operation is carried out. When symmetry operation is carried out, all the
point that constitute the symmetry element will not move but stayed in
the same place throughout the symmetry operation. Some of these
symmetry elements are
i. Symmetry axis in rotation

ii. Plane of symmetry in reflection
iii. Centre of symmetry in inversion
2.0 INTENDED LEARNING OUTCOMES
When you have studied this session, you should be able to
 State what is symmetry

 Discuss what is symmetry elements and symmetry operations
 Carry out symmetry operations on some molecules
 discuss symmetry point group and group theory
 Classify symmetry groups to various classes
 Know the application of symmetry in chemistry
3.0 MAIN CONTENT
3.1 Symmetry Operation
The different types of symmetry operations that are possible in group

theory are highlighted in this section.
3.1.1 Identity Operation.
Identity operation is often denoted as E. In identity operation, the

molecule does not move and all the atoms of the molecule remain at the
same position when identity operation is carried out. It is significant to
state that all molecule has identity operation and can be achieved by
108
perfuming several operations, which finally returns the molecule to its

original appearance. Fig. 5.2 shows how successive rotation of
cyclopropane at 120  can produce an identity element, E
molecule
Fig. 5.2: Symmetry operations in cyclopropane
In the above operation, rotation of the molecule through an angle of 120

 (i.e C3 operation) for three times, will bring back the original
molecule. This implies that three C3 rotation of the yields = E.
Generally, for n axis of rotation, rotation for n times yields =
3.1.2 Proper Rotation
Proper rotation applied to an n-fold axis of rotation and describes

rotation by 360 /n such that the molecule will be left unchanged. The
various angles that are associated with different rotation are shown in
Table 5.1. It significant to note that rotation at 2 x (2π/6) gives = ,
rotation at 3 x (2π/6) gives = , rotation at 4 x (2π/6) gives =
, rotation at 5 x (2π/6) gives and rotation at 6(2π/6) gives =
E. Generally, Cn operation generate n operations given by
, , , ¸ … ( ). For example, ammonia which has C3
axis. Proper rotation operation on ammonia will create three group
namely, , ( ).
Table 5.1: Angles associated with some proper rotation symmetry

Symmetry operation Angle of rotation in Angle of rotation in
degree radian
C1 360 2π
C2 180 3 x (2π/6)
C3 120 2 x (2π/6)
C4 90 2π/4
C5 72 2π/5
C6 60 2π/6
3.1.3 Reflection
If reflection about a mirror plane gives the same molecule/object back

then there is a plane of symmetry. Reflection can be achieved through
three different types of plane. Reflection through vertical plane (σv)
contain the principle axis. Reflection through horizontal plane (σh) are
perpendicular to the principle axis while reflection through dihedral
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CHM 307 MODULE 3
planes (σd) contain the principle axis and bisect two C2 axis. The
different types of reflections are illustrated in the Fig. 5.3below,
Fig. 5.3: Different types of reflections
When mirror plane is operated n times, we have σn. This will give E if n
is even and gives σ when n is odd.
3.1.4 Improper Rotation
Improper rotation is a combination of two operations, proper rotation Cn

and reflection, σ. . Improper rotation is designated as S n, which indicate
n fold rotation, followed by reflection through the rotation axis.
Example of improper rotation operation on methane is shown in Fig. 10
below
Fig.5.4: Improper rotation (S4) in methane
3.1.5 Inversion
Inversion through the centre of symmetry leaves the molecule

unchanged. Inversion consists of passing each point through the centre
of inversion and out to the same distance on the other side of the
molecule. If a line drawn from one side of an atom in a molecule passes
through the centre into the opposite side and produce equivalent point,
then the operation is inversion. Fig. 11 below show inversion operation,
i on XeF4
110
Fig. 5.5: Operation of inversion on XeF4
3.2 Symmetry Point Group
All symmetry elements (lines, point or plane) will intersect at a given

point. This makes it possible to classify molecules based on their
symmetry. The collection of symmetry element present in a molecule is
called point group. For example, the point group for water is C2V and
consist of identity element, E, two fold rotation axis, C2 and two
reflection planes,  and *. The point group for a square molecule
(such as tetraferric xenon and tetracynonickel are shown below (D4h)
Hexagonal molecule such as benzene has the symbol, D6h. The number
indicate the order of the principal axis. The lower-case subscript, h
indicates that there is n (equal to 6 for benzene) C2 (nC2) at right angle
to the principal Cn axis.
Point group symmetry is widely used in spectroscopy, quantum and

crystallography chemistry. An individual point group can be represented
by a set of symmetry operations, which include,
i. E: The identity operation

ii. Cn : rotation by 2π/n angle
iii. Sn : Improper rotation defined as the rotation at 2π/n angle
followed by reflection in the plane perpendicular to the axis
iv. h: Horizontal reflection plane (perpendicular to the principal
axis)
v. v : Vertical reflection plane (contain the principal axis)
vi. d: Diagonal reflection plane (contain the principal axis and
bisect the angle between two C2 axes perpendicular to the
principal axis) where n is an integer and the principal axis is the
Cn axis with the largest value of n. A molecule is said to belong
to a symmetry point group if it is unchanged under all the
symmetry operations of the given group. Some properties of a
molecule (such as vibrational, electronic and vibronic states,
normal vibrational modes, orbital) may show similarity or
111
CHM 307 MODULE 3
differences in behaviour under symmetry operations of the

molecule point group. This behavior coincide with irreducible
representation or irreducible character. All irreducible
representations of the symmetry point groups may be found in the
corresponding character table.
3.3 Classification of symmetric point group
Generally, symmetric point groups can be classified into the following

classes,
3.3.1 Non-Axial Symmetries:
Non axial symmetries consist of C1, Ci and Cs. C1 has only one
symmetric operation, which is E. This group has an order of 1,
indicating that symmetric operations (except E) such as proper rotation,
reflection, mirror and others cannot be carried out. Example of molecule
in this class is HCFBrCl. Ci group has two symmetric operations (E, i)
and an order of 2. Example of molecule in this group is C2H2F2Cl2,
which has an inversion centre. Cs group has two symmetric operations
(E, ) and an order of 2. Example of molecule in Cs class is CH2BrCl,
which has a mirror plane.
3.3.2 Cyclic symmetries
This group consist of the cyclic group (Cn), the pyramidal group (Cnv)
and the reflection group (Cnh) and the improper rotation group (Sn).
Compounds in these classes have only one proper or improper rotation
axis.
The cyclic group (Cn) has an order equal to n and defines a rotation
through an angle of 2π/n. The symmetry elements for C n are
, , , , …… . Example of molecule in this class is
C2H4Cl2.
The pyramidal group is characterized by symmetric element, E, Cn and

n and the symmetry operations are , ( = 1, 2, 3 … , −
1) n . The order of Cnv group is 2n. For example, ammonia
belongs to C3v group. It has C3 ( , , ) axis and three mirror planes,
3 (i.e,  , , ,, ).
The reflection group (Cnh) has symmetry elements equal to E, Cn, h and
Sn. Therefore symmetry operation for this group will yield {E, Cnk(k=1,
… ,n-1), σh, σhCnm(m=1, … ,n-1)}. The order of Cnh group is 2n and
C2H2F2 is an example of a molecule in this group. This molecule has C2h
point group.
112
For the Sn group, n can only be, 4, 6, 8, 10…… and the symmetry
elements are E and Sn while the symmetry operations are {E, Snk(k=1,
… ,n-1)}. The order of Sn group is n. For example, the point group of
1,3,5,7 -tetrafluoracyclo octatetrane is S4.
3.3.3 Dihedral Symmetry
The dihedral symmetry group includes the dihedral group (Dn), the
prismatic group (Dnh) and the antiprismatic group (Dnd). The symmetry
elements for the Dn group are E, Cn, and nC2 (σCn) and the symmetry
operation are [E, Cnk(k=1, … ,n-1), nC2] while the order is 2n. Example
of molecule in this group is [Co(en)3]3+ which is D3.
The Dnh group has symmetry elements, E, Cn, σh,and nC2 (σCn) and the
corresponding symmetry operation are {E, Cnk(k=1, … ,n-1), ?h,
Snm(m=1, … ,n-1), nC2, nσv} while the order of the group is 4n. Benzene
is an example of molecule in this group and has D6h point group.
The symmetry elements for the anti-prismatic point group (Dnd) are E,
Cn, σd, and nC2 (σCn) and the corresponding symmetry operation are {E,
Cnk(k=1, … ,n-1), S2nm(m=1, … ,2n-1), nC2, nσd. The order of the group
is 4n. C2H6 is a D3d and is an example of molecule in this group.
3. 3.4 Polyhedral Symmetry:
This class includes T, Th, Td, O, Oh, I and Ih, which have more than two
high-order axes. They can further be classified into cubic (which include
the T, Th, Td, O and Oh groups) and icosahedral (which include the I and
Ih groups) point groups
The cubic groups do not have a C5 proper rotation axis and consist of
T, Th, Td, O and Oh groups The symmetry elements for the T group are
E, 4C3, and 3C2 and symmetry operations are {E, 4C3, 4C32, 3C2} while
the order of the group is 12. For Th group, symmetry elements are E,
3C2, 4C3, i, 4S6 and 3σh and symmetry operations are {E, 4C3, 4C32, 3C2,
i, 4S6, 4S65, 3σh. The order of Th group is 24. For Td group, symmetry
elements are E, 3C2, 4C3, 3S4 and 6σd and the symmetry operations are
{E, 8C3, 3C2, 6S4, 6σd. The order of Td group is 24 and CCl4 is an
example of Td molecule. Symmetry elements for the O group are E, 3C4,
4C3, and 6C2 and the corresponding symmetry operations are {E, 8C3,
3C2, 6C4, 6C2} while the order of O group is 24.
For Oh group, symmetry elements are E, 3S4, 3C4, 6C2, 4S6, 4C3, 3σh,
6σd, and i. The symmetry operations are {E, 8C3, 6C2, 6C4, 3C2, i, 6S4,
8S6, 3σh, 6σd}The order of Oh group is 48.For example, the point group
of SF6 is Oh.
113
CHM 307 MODULE 3
The icosahedral groups, which consist of the I and Ih groups have C5

proper rotation axis and the include the I and Ih group. The symmetry
elements for the I group are E, 6C5, 10C3, and 15C2while its symmetry
operations are {E, 15C5, 12C52, 20C3, 15C2}. The order of I group is 60.
For Ih group, symmetry elements are E, 6S10, 10S6, 6C5, 10C3, 15C2 and
15σ and symmetry operations are {E, 15C5, 12C52, 20C3, 15C2, i, 12S10,
12S103, 20S6, 15σ. The order of Ih group is 120.For example, the point
group of C60 is Ih. It can be shown that for a group containing a C5
operation (icosahedral group), the under listed functions are correct.
1
 = 1 + 5 = 1.61803 = −2 144°
2
1
 = 1 − 5 = −1.61803 = −2 72°
2
  = 1+    = 1+  . ℎ ,   = −1
2 144° + 2 72°, ℎ ,  +  =1
The Linear group
This class includes C∞v and D∞h, which are the symmetry of linear
molecules. The symmetry elements for the C∞v are E, C∞ and ∞σ v. CO,
HCN, NO, HCl are examples of molecules in this class. For the Dσh
group, symmetry elements are E, C∞ ∞σv , σh, i, and ∞C2. Example of
molecules in this point groups are CO2, O2 and N2.
3.4 Properties of Symmetry Group
Generally, the basic properties of a group are
i. Associativity: All the elements in the group must satisfy the law
of associativity, which can be expressed as (AB)C=A(BC).
ii. Closure: If two elements A and B are in the group G, then the
multiplicity of these two elements, C, is also in this group.
iii. Identity: The group must contain such an element E that
ER=RE=R
In group theory, it refers to the operation identity E. Because any
molecule or substance must at least have the symmetry element
E.
iv. Inverses: If A is an element in group G, there must be another
element A-1 in group G that satisfies AA-1= A-1A=E.
3.5 Application of Symmetry and Group Theory
Symmetry can be used to predict numerous chemical properties of

molecules such as dipole moment and allowed spectroscopic transition
such as prediction of intra red or Raman active vibrations in a molecule;
114
Group theory, which classifies molecules to unique symmetry groups

offers outfits for studying molecular orbitals with references to methods
such as Huckel method, ligand field theory and the Woodward
Hoffmann rules. The structure and behavior of molecules and crystals
depend on their different symmetries, group theory is an essential
theoretical tool to aid the prediction of some characteristic properties of
molecules. Solutions obtained from quantum mechanics for some
chemical problems ends with complicated mathematics but those from
group theory are simplified and easy to follow.
Crystal symmetry is useful in describing crystallography symmetry in

bulk materials. Apart from computational chemistry calculations, there
are practical techniques that can be used to assess molecular symmetry.
X-ray crystallography is one of such methods
Self Assessment Exercises
1. What are the irreducible and reducible symmetry elements for the
C4v point group
2. How many line of symmetry has cyclopropane. Show this using
an equilateral triangle
3. Draw the following shapes and identify the number of lines of
symmetry for each of them: rhombus, square and a scalene
triangle.
4. List the symmetry elements for water molecule
5. What is the symmetry elements for tetrachlropalladate,
[ ]
Answer to Self Assessment Exercise
1. The symmetry elements for C4v point group are

, , , ,  , ,  ,, ,  ,  ,, . This consist of eight (8) reducible
elements, which can be reduced to five (5) irreducible elements
as follows, ≡ , 2 , , 2 2
2. Cyclopropane has three lines of symmetry. This can be
represented as,
3. The number of line of symmetry are as follows,
115
CHM 307 MODULE 3
4. Water molecule belongs to C2V point group. The symmetry

elements are , ,
5. The symmetry elements for tetrachlropalladate are E, i, C4, 4C2,
S4, σh, 2σv and 2σd
4.0 CONCLUSION
A symmetry operation is an act upon whose execution the resulting

molecular appearance is indistinguishable from the one before that
operation was executed. The presence of symmetry in a molecule greatly
reduces the effort in predicting the nature of some molecular properties.
Although visual inspection can reveal the presence (or lack) of
symmetry in a given molecule, a systematic approach to characterize
that symmetry is desirable. The theory of point groups provides one
such approach.
5.0 SUMMARY
A point group is a collection of symmetry operations that satisfy, as a

group, certain characteristics and leave a point in a molecule unaffected.
Based on the type and number of symmetry operations present, a
molecule can be classified to belong to a certain point group. Regardless
of the number or type of symmetry elements (or operations) a given
molecule possesses, every molecule has an identity element (or an
operation), E. This symmetry operation is no more than doing nothing.
That is, every atom in a given molecule transforms into itself upon
identity operation
116
6.0 TUTOR MARAKED ASSIGNMENT
(1) What are the applications of symmetry in crystallography and in

organic chemistry (4 minutes)
(2) Draw the structure of cyclobutene and indicates all the symmetry
ele,emts when the molecule is progressively rotated at 90  until
identity element is obtained. 6 minutes)

India

Banwell, C. N. (1983). Fundamental of molecular spectroscopy,



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117
CHM 307 MODULE 3



118
MODULE 3
UNIT 2 HEAT CAPACITY OF SOLID AND CRYSTALS
1.0 Introduction
2.0 Intended Learning outcome
3.0 Main Content
3.1 Theoretical Consideration of Heat Capacity
(ii) Class Activity
5.0 Conclusion
6.0 Summary
1.0 INTRODUCTION
In 1819 by French physicists Pierre Louis Dulong and Alexix Therese

Petit, proposed a thermodynamic law and states the classical expression
for the molar specific heat capacity of certain chemical elements.
Experimentally the two scientists had found that the heat capacity per
weight (the mass-specific heat capacity) for a number of elements was
close to a constant value, after it had been multiplied by a number
representing the presumed relative atomic weight of the element. These
atomic weights had shortly before been suggested by John Dalton and
modified by Jacob Berzelius.
In modern terms, Dulong and Petit found that the heat capacity of a
mole of many solid elements is about 3R, where R is the modern
constant called the universal gas constant. Dulong and Petit were
unaware of the relationship with R, since this constant had not yet been
defined from the later kinetic theory of gases. The value of 3R is about
25 J/K, and Dulong and Petit essentially found that this was the heat
capacity of certain solid elements per mole of atoms they contained.
The modern theory of the heat capacity of solids states that it is due to
lattice vibration the solid and was first derived in crude form from this
assumption by Albert Einstein in 1907. The Einstein soldi model thus
gave for the first time a reason why the Dulong–Petit law should be
stated in terms of the classical heat capacities for gases.
119
CHM 307 MODULE 3
3.0 MAIN CONTENT
3.1 Theoretical Consideration of Heat Capacity
As sated before, heat capacity is defined as the amount of heat absorbed

per unit change in temperature. Thermodynamics reveals that the heat
absorbed at constant volume is called the internal energy change.
Therefore, the heat capacity at constant volume can be written as,
=
If the substances is a gas, the physical state of the compound and the
conditions heat is transferred (i.e constant volume or constant pressure).
However, for solid, these factors are relatively negligible, hence we can
state that the heat capacity of solid is
= 6.1
Simple harmonic oscillator model can be applied to described heat

capacity of a solid. If a solid is considered to be a three-dimensional
lattice arrangement of atoms held (near equilibrium) together by strong
forces of interaction. The force on the atom is said to be simple
harmonic if there is a deviation from the equilibrium position.
Consequently, when there is no displacement, the force is zero
indicating that when the deviation is small, the force is proportional to
the deviation. Any solid that obeys this model can be said to compose of
harmonic oscillators. For example, in a cubic crystal, the atoms is free to
oscillate in three dimensions.
In a one dimension, the average energy of a harmonic oscillator is kT (k

= Boltzmann’s constant). Therefore, for three dimensions, the average
energy will be 3kT. For N number of atoms in the lattice, the internal
energy, U = N(3kT). If this is divided by Avogadro’s number (A = 6.025
 1023), we have,
= =3 6.2
where n is the number of moles ( = ), U is the internal energy, k is

the Boltzmann constant and T is the temperature is Kelvin unit.
Therefore, the heat capacity per unit mole can be defined as,
= =3 =3 6.3
Since = , then,
120
( )
= =3 6.4
Therefore, it can be stated that the heat capacity of a solid at constant

pressure (Cp) is equal to 3R (which is approximately equal to 6 calories
per degree Kelvin). This value is called Dulong and Petit value. At room
temperature (300 K), most solid obey Dulong and Petit law. However, at
low temperature, the most solid witness deviation from this law. For
example, a plot of heat capacity of metallic silver as a function of
temperature is shown in Fig. 6.1
Fig. 6.1: Variation of heat capacity of silver metal with temperature
The shape of the curve for T near zero reveals that the heat capacity is
proportional to a power of T, that is T² or T³. Dulong and Petit found
that the heat capacity of amole of many solid elements is about 3R,
where R is the modern constant called the universal gas constant. An
equivalent statement of the Dulong–Petit law in modern terms is that,
regardless of the nature of the substance, the specific heat capacity of a
solid element (measured in joule per kelvin per kilogram) is equal to
3R/M, where R is the gas constant (measured in joule per kelvin per
mole) and M is the molar mass (measured in kilogram per mole). Thus,
the heat capacity per mole of many elements is 3R.Planck's law of
distribution of energy for an ensemble (collection) of harmonic
oscillators gives the average energy E as,
121
CHM 307 MODULE 3
ћ
= ћ 6.5
where ћ = and is called reduced Planck constant, is the

characteristic frequency (circular) of oscillation. depends on the
nature of the solid. Temperatures that makes ≫ ћ , approximate the
energy value (according to equation 6.5) to kT. Generally, from
definition of internal energy, that is the total energy a molecule
possesses, that is, = ∑ , we have
ћ
= ∑ = ћ 6.6
ћ
= / = ∑ = ћ 6.7
ћ
= = ћ ћ ћ
6.8
Equation 6.8 can be re-arranged into the form shown in equation 6.9
ћ ћ
= ћ
6.9
Division of the numerator and denominator of equation 6.8 by

ћ
exp − 1 , leads to equation 6.10
ћ ћ
= ћ
6.10
Attempt to obtain the limit of this expression as T→0 will produces

ambiguous result of ∞/∞. However, the application of l'Hospital's Rule
two times will finally produces the result that the limit of Cp is zero as
T→0.
As observed from Fig. 6.1, the empirical heat capacity curve for silver
seems to be proportional to T² or T³ for small values of T. The graph of
the quantum mechanical heat capacity function derived above indicates
that for values of T near zero the heat capacity function is zero and flat
as shown in Fig. 6.2.
122
Fig. 6.2: Variation of heat capacity of metallic silver with

temperature ranging from 0 to 350 K
ћ
The function, has the same dimension as temperature and can be
denoted as, .  is called the Einstein temperature. Consequently, the
ћ
heat capacity function can be written by replacing in equation 6.10
with , which gives
 
= 
6.11
Also, by replacing /T with z, we have,

( )
=[ ( )]
6.12
= ln(3 ) + 2 ln( ) − 2ln[(1 − exp(− )] 6.13
The implication of equation 6.13 is that ln (Cp)→−∞ as z→+∞; i.e.,
Cp→0 as T→0.
(i) Self Assessment Exercises

ћ ћ
1. Given t Given that = ћ

, Use l'Hospital's Rule to
show that Cp → 0 as T→0

2. How much energy (in J) is lost when a sample of iron with a
mass of 25.7 g cools from 75 to 22 C (Specific heat of iron, C=
0.450J/g/C.
123
CHM 307 MODULE 3
3. What is the specific heat of lead in J/g//C, if it takes 97.6 J97.6 J

to raise the temperature of a 75.2 g of block by 10.0C?
4. What is the heat capacity of 83 g of mercury? The specific heat of
mercury = 0.14 J/g/C
5. In the lab, an experimenter mixes 9.0 g of water (initially at 23.4
C) with 80 g of a solid metal (initially at 350 C). At thermal
equilibrium, he measures a final temp of 55.4 C . What
must the specific heat of the metal be?
Answers to Self Assessment Exercise
ћ
1. The term, 1 − exp − can be ignore because it approaches
the limit of 1 as T→0, thus equation 6.10 becomes
ћ −ћ
=3
ћ
Since the term, has the same dimension with temperature, it can be
replaced with  and the above equation becomes,
 −
=3
When T goes to zero the above expression goes to ∞/∞. By l'Hospital's
Rule we should consider the limit of the derivatives of the numerator
and denominator. Thus
1
3 (2  1 
=6 
 
−
The above expression gives to ∞/∞, at the limit the temperature tends to
zero. However, the l'Hospital's rule must be applied again, which gives
1   6
6  =

From the above, Cp → 0 as T→0.
2. Given
Mass of iron m =25.7 gm = 25.7 g

Change in temperature ΔT=22.0 −75.0 =−53 C
Specific Heat of iron C= 0.450J/g/C
The heat loss is given as, Q=mCΔT = 25.7 g(0.450J/g/C)(-53C) = -
612.945 J
124
Therefore, the energy loss is 612.945 J
3. Given:
Heat Energy Q=97.6 J
Change in Temperature ΔT=10 C
Mass of the lead m = 75.2 gm =75.2 g
But Q = mCT, indicating that C is given as,
97.6
= = = 0.1298 /C
∆ (75.2 )(10 C)
Therefore, the specific heat capacity of lead is 0.130 J/g/C
4. Heat capacity, C is related to specific heat capacity as follows,
= × ℎ = 83 (0.14 /( C)
= 12 J/C
5. The first step involves calculating the energy gained by the water,
thus,
= 9 × 4.186 (55.4 − 23.4) = 1205.6
∆ = (350 − 55.4)C = 294.6 C
Consequently, 1205.6 J of energy was gained by the metal. Hence,
1205.6 = ∆ and
1205.6 1205.6
= = = 0.0512 / /
∆ (80 )(294.6 C)
(ii) Class Activity
(1) A 0.500 kg aluminium pan on a stove is used to heat 0.250 liters
of water from 20.0 C to 80.0C (a) How much heat is required? What
percentage of the heat is used to raise the temperature of (b) the
pan and (c) the water? (10 minutes)
4.0 CONCLUSION
Crystal solids behaves differently from ordinary solid indicating that

molecular vibrations in crystals also differs. Specific heat is an intrinsic
property of a substance that is the measure of heat energy required to
raise a unit mass of a substance by one-unit degree. Specific heat can be
used to solve for the heat absorbed or heat loss by the substance
depending on the change in temperature..
5.0 SUMMARY
This study section analysed theoretical framework for the prediction of

heat capacity of solid crystal. Unlike gases and liquid, conditions of
operation (that is constant pressure or constant volume) is negligible in
solids. There are two basic models that explain the heat capacity of
solid. These are Dulong and Petit law and Einstein law. Both laws
reveals that as the temperature tends to zero, the heat capacity also tend
125
CHM 307 MODULE 3
to zero and that heat capacity has some exponential relationship with
temperature.

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CHM 307

ATOMIC AND MOLECULAR STRUCTURE AND SYMMETRY

Course Team: Dr. N.A.A. Babarinde (Developer/Writer)-

NATIONAL OPEN UNIVERSITY OF NIGERIA

National Open University of Nigeria

Theories of molecular structure can be generally divided into classical

Atomic and molecular symmetry (CHM 307) is a three credits unit

This course is aimed to bring the student to the knowledge of

The book is concluded by discussion of heat capacity of crystal solid.

i. Understand the Schrodinger equation, its derivation from first

WORKING THROUGH THIS COURSE

The course is structured into five models. Modules 1 to 3 consist of two

You will be provided with the following materials:

Study Unit 1: The Schrödinger equation

Study Unit 1: Molecular Spectroscopy

Study Unit 1: Symmetry and Group Theory

Study unit 1 (in module 1) introduces the Schrodinger equation and

In module 2 study unit 1, molecular spectroscopy is introduced with

In study unit 2 of module 2, the concept of coupling with special

In study unit 1 of module 3, symmetry and group theory are discussed

Finally, in study unit 2, heat capacity is defined. Models (Dulong and

REFERENCES AND FURTHER READNGS

Textbooks referred to in the development of each units are presented at

Allinger, N. L (2010). Molecular structure: Understanding steric and

Atkins, P. and De Paula, J. (2010). Atkins’Physical chemistry. 9th

Banwell, C. N. (1983), Fundamental of molecular spectroscopy,

Demaison, J., Boggs, J. E. and Csaazar, A. G. (2010). Equilibrium

Dhaduk, B. (2019). A textbook of physical Chemistry. Lambert

Engel T. and Reid, P. (2005). Physical chemistry. Pearson Cummings.

Hofmann, A. (2018). Physical Chemistry essentials. Springer

Job, G. and Ruffler R. (2019). Physical chemistry from different angle.

Lagana, A and Parker, G. A. (2018). Chemical reactions. Springer

Monk, P. (2004). Physical chemistry: Understanding the Chemical

Struve, W. S. (1989). Fundamental of molecular spectroscopy. John

Struvel, W. S. (1987), Fundamental of molecular spectroscopy Springer

Tamvakis, K. (2019). Basic quantum mechanics. Springer International

Telxeira-Dias, J. J. C. (2017). Molecular physical chemistry. Springer

This course is presented in three different modules. Each module

HOW TO GET THE MOST FROM THE COURSE

Student are expected to comprehends best information out of this course

Unit 1: The Schrodinger Equation…………………. 1

Unit 1: Molecular Spectroscopy………………….... 66

MODULE 3……………………………………. 107

Unit 1 Group Theory and Symmetry……………… 107

UNIT 1 THE SCHRODINGER EQUATION

Atom consists of proton, electron and neutron. The proton is positively

atom is concentrated in the central nucleus (which contains proton and

In 1913, Niels Bohr offered explanation to the Rutherford theory

Bohr found that when hydrogen gas is heated, it emits electromagnetic

EHigher - ELower = hv 1.2

Although Bohr model was satisfactory in explaining the hydrogen atom,

In quantum mechanics, uncertainty principle is any of the variety

2.0` INTENDED LEARNING OUTCOMES (ILOS)

 Comprehends developmental stages of quantum chemistry and

3.0 MAIN CONTENT

3.1 The time independent Schrödinger equation

This is an equation that describes how the quantum state of a system

Differentiating equation 1.10 with respect to x, we have;