Subject Chemistry

Paper No and Title Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding,

Electronic Spectra and Magnetic Properties of Transition
Metal Complexes)
Module No and Title 11, Electronic spectra of coordination complexes III

Module Tag CHE_P7_M11

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 11: Electronic spectra of coordination complexes III
 TABLE OF CONTENTS
1. Learning Outcomes

2. Introduction

3. Spinning of an electron

4. Orbital motion of an electron

4.1 Defining an orbital

4.2 Orbital

5. Spin-Orbit coupling

4.1 What is spin-orbit coupling?

4.2 Free ion terms

6. Summary

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 11: Electronic spectra of coordination complexes III
 1. Learning Outcomes
After studying this module, you shall be able to

 Know the difference between spinning and orbital motion of an electron

 Learn various factors influencing the spin orbit coupling
 Analyze various free ion terms for different configurations
 Understand the orbital in an atom along with orbital motion

2. Introduction
For multi-electronic atoms and ions, the spin and orbital motion of various electrons are coupled
together by spin-orbit coupling or L-S coupling or Russell-Saunders coupling. In this practice the
total angular momentum represented by L and total spin angular momentum given by S, combine
together to generate a new quantum number given by J.

3. Spinning of an electron
A spherical body rotating about a fixed axis that passes
through a point at the center of the sphere represents a
model that how electron behaves in an atom. This means an
electron always spins on its own axis either in a clockwise
or anticlockwise direction (figure 1). The concept was first
introduced by Uhlenbeck and Goudsmit. The spinning of
electron about its own axis gives rise to spin quantum
number represented by ms. It is required to fully specify the
ambience of an electron in the atom. The spin quantum
number can have two values, +1/2 if an electron is spinning
clockwise and -1/2 if it is rotating anticlockwise. This
spinning of an electron generates an intrinsic angular
momentum related to it. The splitting of many spectral lines
in the electronic spectra can be analyzed with the presence
of spin angular momentum. An electron gyrating about the
nucleus experiences the magnetic field produced by the
nucleus which is circling about it in its own casing. This
magnetic field then operates upon the electron’s own spin
magnetic moment to create sub states in terms of energy.

Figure 1. The spin of electron on its own axis

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 11: Electronic spectra of coordination complexes III
 The angular momentum of a spinning particle is mathematically symbolized by a vector (figure
2). For the electronic spin, vector length is given by [s(s + 1)]1/2 where s is the spin quantum
number. The vector can acquire only certain values representing specific orientations in space. In
case of multi-electronic systems, the spin momentum of various electrons couple together to give
a vector sum represented by the symbol S. Associated with S is Ms which represents the
magnitude of orientation of the spin. In simple terms S is the quantum number associated with the
length of the total spin and Ms is the quantum number associated with the orientation of total spin
relative to the z axis.

Possible values of Ms = S, (S -1),..., (-S)

Figure 2. Angular momentum of the spinning electron represented by the vector in clockwise and
anticlockwise direction

4. Orbital motion of an electron

4.1 Defining an orbital

An orbital can be suggested as a space around the nucleus where electron can move around. Since
due to uncertainty in determining the velocity and angular momentum persists for any electronic
movement, an orbital can better be discussed in terms of probability. Hence it is that path
surrounding the nucleus where the probability of finding the electron is maximum (figure 3).

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 11: Electronic spectra of coordination complexes III
 Figure 3. Representing an orbital within the atomic system

Since the electron shows dual nature, it behaves as particle and also as a wave, hence the
electronic movement can be represented in terms of a wave function and a wave equation.
Talking in terms of polar coordinates, the wave function splits into two parts, namely radial part
and angular part. The radial part gives an idea about the probability finding electron at a distance
‘r’ from the nucleus. In case of a radial node, the radial part of a wave function changes sign and
when we have an angular node, the angular part of the wave function changes sign. The number
of nodes in an orbital is given by:

Number of angular nodes = l

Number of radial nodes = (n – 1 – l)

Total number of nodes = n – 1

Figure 4 shows various atomic orbitals present in the hydrogen atom. The electronic wave
functions are deciphered in terms of radial and angular probability plots

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 11: Electronic spectra of coordination complexes III
 Figure 4. Representing the various atomic orbitals of the hydrogen atom

4.2 Orbital motion

Classically, rotational motion refers to the rotation of an object about a fixed point. An electron in
an atom moves in a circular path with the fixed radius about the nucleus. This rotational motion
of an electron in an orbit, around the nucleus, leads to origin of orbital angular momentum.
Orbital angular momentum can be visualized in terms of electron with mass m revolving around
the nucleus in an orbit of the radius r and angular velocity v. the expression is given as
L= mvr, where L is the angular momentum of the system. The orbital angular momentum can be
represented by a vector. Figure 5 shows the vector representation of the electron rotating in the
CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra
and Magnetic Properties of Transition Metal Complexes)
Module 11: Electronic spectra of coordination complexes III
 Bohr’s orbit. The angular momentum vector is always directed towards the direction where it is
perpendicular to the plane in which circular motion of the electron in its orbit is taking place.
Angular momentum is represented by the vector length. The features important in the case of
classical representation for the angular momentum are: (1) that angular momentum can be
represented by a vector whose direction is related to the sense of the direction of rotation; (2) that
the representation of the vector can be conveniently placed on the axis of rotation; and (3) that the
length of the vector is proportional to the absolute magnitude of the angular momentum.

In case of multi-electronic systems, the orbital angular moments of various electrons couple
together to give the resultant orbital angular momentum of the system. Thus total angular
momentum quantum number represented by L can be given as

L = (l1+l2), (l1+l2-1), (l1+l2-2)…………(l1-l2)

The quantum number Ml describes the component of L in the direction of the magnetic field for
an atomic state. The values of L correspond to the atomic states which can be described in terms
of S, P, D, F,………

Ml = 0, ±1, ±2, …….., ±L

Figure 5. The vector representation of the electron rotating in the bohr’s orbit. The direction of
angular momentum vector is perpendicular to the plane defined by the circular motion of the
electron in its orbit.

5. Spin – Orbit coupling

5.1 What is spin-orbit coupling?

The electrons in any atom behave in a very similar manner in the sense of having an orbital as
well as spin motion. Till this point we have seen that the orbital as well as spin motion of various
electrons in a system have to added so as to give resultant total orbital and spin angular moments.
Now, we will see that, the spin and angular moments of the electrons also couple together by the
process called spin-orbit coupling. This coupling further gives rise to a new quantum number
deciphered as J which is called total angular momentum quantum number. The quantum number J
can have following values
CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra
and Magnetic Properties of Transition Metal Complexes)
Module 11: Electronic spectra of coordination complexes III
 J = (L+S), (L+S-1), (L+S-2), ………..,|L-S|

5.2 Free ion terms

The atomic states characterized by the values of L, S, J are referred to as free ion terms or
Russell-Saunders terms. This is because they actually describe the individual atoms or ions which
are ligands free. They are also specified as term symbols. Term symbols are represented in the
form where L is designated along with the value of spin multiplicity on the left superscript and
value of J on the right subscript.

(2S+1)
LJ = Term symbol

L = Total orbital angular momentum quantum number

(2S+1) = Spin multiplicity

J = Total angular momentum quantum number

For example the term symbol 3P2 represents the state in which L=1 and the spin multiplicity is 3,
whereas also the value of J is 2.

Free ions terms are very important in analysis of the absorption spectra of the coordination
compounds. Spin orbit coupling acts to split up free ion terms into states of different energies. For
example 3P term splits up into states of three different energies as shown below in figure 6.

Figure 6. Various energy states for p2 configuration of the carbon atom

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 11: Electronic spectra of coordination complexes III
 A single electronic state can gives rise to various free energy terms and term symbols. These
terms have different energies which further suggest the difference in electronic interaction for the
different terms. For example p2 configuration can have three different free ion terms which are
distinct in terms of their energies. The table 1 shows various free ion terms for different electronic
configurations of the d orbital. In order to find a term of lowest energy following rules needs to
be followed:

Table1. Free ion terms for dn configurations

1) The ground state is one with the highest spin multiplicity

2) If two or more terms have the same value of spin multiplicity, ground state is one with
maximum value of total orbital angular momentum quantum number that is represented by L. For
example in table, d2 configuration has two terms with same highest spin multiplicity of 3. These
are 3P and 3F. Out of these, 3F term will be lower in energy since it has greater value of L.

3) For the sub-shell that are less than half filled, the state of lowest J value is the term of lowest
energy and for the terms that are more than half filled the term with maximum value of J is the
term of lowest energy. For example in case of p2 , the term 3P0 will be lowest in energy.

In order to interpret the electronic spectra of coordination complexes, it is often required to find
out the term of lowest energy. Given below is an example of d3 configuration in octahedral
geometry. The various steps involved are as follows:

1) Represent the valence electrons in various energy shells.

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 11: Electronic spectra of coordination complexes III
 2) Calculate the total number of unpaired electrons. In this case it is 3. Therefore, the spin
multiplicity will be (2S+1) where S = 3(1/2) = 3/2. Thus spin multiplicity is

(2(3/2) +1) = 4

3) Now find the maximum possible value of Ml which will give the value of L. In this case the
maximum possible value of Ml will be the one that we will get by adding the ml values of
individual electrons. Thus

Maximum Ml = ml1+ ml2+ml3 = 2+1+0 = 3

This value corresponds to F term

L=0 1 2 3 4 5

Free Ion Term = S P D F G H

4) Now the lowest value of J in this case will determine lowest energy term since the shell is less
than half filled.

J = (L+S), (L+S-1), …………., |L-S|

J = (3+3/2), (3+3/2-1), ……….., (3-3/2) = 9/2, 7/2, 5/2, 3/2

Thus in this case the lowest energy term will have J value of 3/2

Now the complete term symbol of the lowest term can be given as

4
F3/2

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 11: Electronic spectra of coordination complexes III
 6. Summary

 Electron always spins on its own axis either in a clockwise or an anticlockwise direction.
This spinning of electron gives rise to spin quantum number represented by ms.
 The spin quantum number can have two values namely +1/2 when an electron is spinning
clockwise and -1/2 when it is rotating anticlockwise.
 Spinning motion of an electron gives rise to an intrinsic angular momentum associated
with it.
 The splitting of many spectral lines in the electronic spectra can be analyzed with the
presence of spin angular momentum.
 The angular momentum of a spinning particle is mathematically symbolized by a vector.
For the electronic spin, vector length is given by [s(s + 1)]1/2 where s is the spin quantum
number.
 The orbital angular momentum revolving in a circular path can be represented by a
vector.
 In case of multi-electron system, the orbital angular momentum for various electrons
couple together to give the resultant orbital angular momentum of the system.
 Spin and angular moments of the electrons also couple together by the process called
spin-orbit coupling. This coupling further gives rise to a new quantum number(J) which
is called total angular momentum quantum number.
 Term symbols are represented in the form where L is designated along with the value of
spin multiplicity on the left superscript and value of J on the right subscript.

(2S+1)
LJ = Term symbol

 A single electronic state can give rise to various free energy terms and term symbols.
These terms have different energies which further suggest the difference in electronic
interaction for the different terms.

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 11: Electronic spectra of coordination complexes III