Electronic Spectra of Transition Metal

complexes
[Link]. Third Year Semester-VI
Paper no. XIV

Dr. S B Zangade
Assistant Professor
Department of Chemistry
Madhavrao Patil ACS College, Palam
Dist. Parbhani -431720 (M.S.) India
 Electronic Spectra of Transition Metal complexes

Syllabus
1. Types of electronic transition.

2. Selection rule for d-d transition.

3. Spectroscopic ground state and spectro-chemical series.

4. Orgel energy level diagram for d1 and d9 states.

5. Discussion of electronic spectrum of [Ti (H2O)6]3+ complex ion.

 Introduction

Electronic spectra of transition metal complexes help us to gain an insight into

the structure and bonding in complexes. A blue solution of copper sulphate
becomes dark blue on addition of ammonia solution. Perhaps the nature of ligand
has something to do about it. The stronger NH3 ligands replace the H2O ligands.
Sometimes the same metal displays different colors even with the same ligands in
different crystal fields.
Example: [Co(NH3)6]+2 complex in octahedral field is pink but blue in [CoCl4]2- in
tetrahedral complex.
The blood that flows in our body is red because of complexation of heme
group with iron.
It has been established that colour of complex compounds is because of d-d
transitions, the electron excited from the lower d-orbitals to higher d-orbitals.
Energy from the visible range is absorbed in these radiation. Rest of the radiation
are transmitted. It is the transmitted radiation that form the colour of the substance.
It is important to note that the colour of a substance is not the radiations that
are absorbed but the radiations that are transmitted. The visible (white) light
consist of different colours like VIBGYOR. If substance does not absorb any
radiation, it looks like white while, if absorb all the colours, it looks black
 Basic of Electron-Absorption
In metal complexes, the electron gets excited from lower set of d-orbital to
higher set of d-orbital when visible light is incident on them. As a results of
transition some selected wavelength of visible light corresponding to energy
difference between t2g and eg levels is absorbed. The transmitted light gives
colour to complexes.

Where c is velocity of light and h is Planck's constant.

The extent of intensity of absorption light of particular wavelength (or
frequency) by species in solution can be obtained by Beer Lambert law. If light
of intensity, I0 at a given wavelength passes through a solution, the light
transmitted with intensity, I may be measured by a suitable detector. According
to Beer-Lambert law, the light transmitted and incident light are related as,
 Types of electronic transition
There are mainly four types of electronic transition occur in metal complexes.
1. Ligand to Metal Charge Transfer Transition (LMCT)
If the transfer or migration of electron from ligand to the metal occur then transition is called
as Ligand to Metal charge transfer Transition.
Example: [Cr(NH3)6]+3.
2. Metal to Ligand Charge Transfer Transition (MLCT)
If the transfer or migration of electron from metal to the ligand occur then transition is called
as Metal to Ligand charge transfer Transition.
Example: The ligands such as CN-, SCN-, Pyridine, carbon monoxide etc. which are Pi-
acceptors are able to form Pi-back bonding by accepting electron from metal.
3. Intermetal Charge Transfer
The charge transfer from one metal to other metal called Intermetal charge Transfer
Transition.
Example: K2FeII[FeII(CN)6] in this complexes the transfer from one Fe-metal atom to other
Fe-metal atoms.
4. Interligand Charge Transfer
The charge transfer from one ligand to another ligand called interligand charge transfer
transition. Those ligand which them self may have a chromophore can able to show this type
of transition.
Example: Ligands such –NO2, NO, -N=N-, C=O can show Interligand Charge Transfer
 Basic of Electron-Absorption

Where, A = absorbance, c = molar concentration of absorbing species,

ϵ = constant known as molar extinction coefficient. It is also known as
molar absorptivity (L mol-1cm-1), I = path length through solution (in cm).
The term by A is known as absorbance (or optical density).
The molar absorptivity is a characteristics property of the species that is absorbing
the light and is highly dependent on wavelength. A plot of molar absorptivity
versus wavelength gives a spectrum characteristics of the molecule or ion. This
spectrum provides valuable information about the structure and bonding of the
molecule or ion.
 Spectroscopic Ground state: Term Symbol and LS coupling

The complete information of the electrons in an atom can be obtained from four
quantum numbers. These four quantum number are,
1. Principal Quantum number (n): It determines the main energy level or
shell in which the electron is present. it can have whole number values as.
n = 1,2,3,4……

2. Angular Quantum number (l): It is related to the angular momentum of the

electron. In multi-electron atoms the energy besides depending upon n and also
l value. Corresponding to each value of n, there are n possible values of l as,
l = 0, 1, 2, 3……..(n - 1). The various values of l called subshell are designated
as s, p, d, f…….
Value of l 0 1 2 3 4
Assign to s p d f g
 Spectroscopic Ground state: Term Symbol and LS coupling
3. Magnetic quantum number (ms): It refers to different orientation of the
orbitals in space. For given value of l, ms can have (2l + 1) values as,
ms = -l, -(l-1)……0……+(l+1), +l
Thus if l = 1, m will have 3 values i.e. -1, 0, +1
If l = 2, m will have 5 values i.e. -2, -1, 0, +1, +2
4. Spin quantum number (s): This describe the spin orientation of electron.
Since the electron can spin in two ways i.e. clockwise or counter clockwise, s can
have only two values The values may also be indicating by arrows
pointing up (↑) and down (↓) respectively. It determines the spin angular
momentum.
The distribution of electrons in different levels in an atom is known as electronic
configuration. The filling of orbitals is governed by three well known rules.
1. Aufbau principle: Electrons enter the orbitals of lowest energy first and
subsequent electrons are filled in increasing order of energy i.e. 1s, 2s, 2p, 3s,
3p, 4s, 3d.
2. Paulis exclusion principle: No two electrons in an atom can have the same
value for the four quantum numbers.
 Spectroscopic Ground state: Term Symbol and LS coupling

3. Hund’s rule: when several orbitals of the same energy are available
(degenerate state) the electrons tend to remain unpaired as for as possible i.e. the
electrons tend to retain parallel spins as much as possible, on energy
consideration.
Term Symbol: Spin angular momentum (s) and orbital angular momentum (l)
of the electrons may interact or couple to give a resultant angular momentum for
the entire multi-electron atom. The resultant angular momentum and the energy
of the system is expressed in a Term Symbol.
“Term Symbol are used to indicate the electronic configuration and the resultant
momentum of an atom.” The Term symbol for a particular atomic state is
expressed as,
2S+1L
J
Where, S = Total spin angular quantum number
L = Total orbital angular quantum number
J = Total angular momentum quantum number
(2S+1) is called the spin multiplicity of the state (arrangement).
Spectroscopic Ground state: Term Symbol and LS coupling

Just as we have the symbols s, p, d, f for l =0, 1, 2, 3 the different values of L

are assigned by S, P, D, F, G, H, I etc. Thus the state S represents L =0, P
represents L =1 and so on.

L 0 1 2 3 4 5 6 7
State S P D F G H I K

LS or Russell Saunders Coupling

1. LS coupling scheme applicable to systems in which spin orbital interaction
are relatively small or negligible.
2. The individual orbital angular momenta of electrons couple (interact) to give
a resultant angular momentum, L for the state.
3. The individual electron spin momenta also couple to give a resultant spin
momentum, S.
4. The L and S values together determine the total angular momentum, J.
 Spectroscopic Ground state: Term Symbol and LS coupling

Rules for determining the term symbol.

A. Determine total spin angular momentum (ss coupling).
For a single electron we know spin quantum number, ms = ½. When two or
more electron present in subshell, then their magnetic fields couple to produce
resultant spin quantum numbers, S. The resultant spin quantum number is
calculated for S1= ½ and S2= ½ as,
S = (S1+S2), (S1+S2-1)……..|S1-S2|
S = (1/2 + 1/2), (1/2 + ½ - 1)…..(1/2 – 1/2)
S = (1) (0)
Spin multicity is given by relation 2S+1 and is written in the upper left hand
corner of the term symbol for the state. The various spin multiplicity are given.
Unpaired electrons s Spin multiplicity (2S+1) State
0 0 1 Singlet
1 ½ 2 Doublet
2 ½+½ =1 3 Triplet
3 ½+ ½ + ½ = 4 Quartet
4 ½+ ½ + ½ + ½ = 2 5 Quintet
Spectroscopic Ground state: Term Symbol and LS coupling
B. Determination of resultant angular momentum (ll coupling)
When two electron with angular momentum l1 and l2 interact, the resultant
angular quantum number, L are given by relationship.
L = (l1+l2), (l1+l2 -1), (l1+l2 -2)………| l1 - l2|
Where modulus sign | | indicates the positive value.
Example: for p orbital or subshell having two electrons (as in carbon).
l1 = 1 and l2 = 1 so that
L = (1+1), (1+1 -1), ………| 1 - 1 |
L = (2), (1)……….|0|
L = D, P…….S
Therefore p2 electrons will represents three energy states, S, P and D
corresponding to L = 0, 1, 2.

Similarly for d2 configuration, l1 = 2 and l2 = 2. How many energy state

possible? (Assignment).
 Spectroscopic Ground state: Term Symbol and LS coupling

C. Spin-orbital or LS coupling
The magnetic effects of the resultant angular momentum, L and the resultant spin
moment S couple together to give new quantum number J called the total angular
quantum number. J values can be obtained by the vectorial combination of L and
S. This is coupling or combination is called as Russell Saunders or LS coupling.
The value of J can be obtained by relationship.
J = (L+S), (L+S-1), (L+S-2)……|L-S|
The value of J is written as subscript in the Term symbol.
We shall illustrate these rules by taking the example of p2 and d2 configuration.
p2-configuration
Step 1
For two p-electrons, l1 = 1 and l2 = 1
L = (1+1), (1+1 -1), ………| 1 - 1 |
L = (2), (1)……….|0|
L = D, P…….S
Hence energy states are S, P and D
 Spectroscopic Ground state: Term Symbol and LS coupling

Step 2
For two p-electrons, the S1 = +1/2 and S2 = +½
S = (S1+S2), (S1+S2-1)……..|S1-S2|
S = (1/2 + 1/2), (1/2 + ½ - 1)…..(1/2 – 1/2)
S = (1) (0)
For S = 1, spin multiplicity (2S+1) = 3 (triplet)
For S = 0, spin multiplicity (2S+1) = 1 (singlet)
Therefore we, have six states corresponding to states S, P and D and corresponding to spin
multiplicity 3 and 1. each can be written as
3S, 3P, 3D, 1S,1P and 1D

Step 3
Calculation of J values
When (A) L =2, 1 and 0 and S = 1 i.e 3D state
(i) When L =2 and S= 1
J = (L+S), (L+S-1), (L+S-2)……|L-S|
J = (2+1) (2+1-1) (2+1-2)
J = (3) (2) (1)
Complete spectroscopic Term symbol 2S+1LJ 3D3, 3D2, 3D1
 Spectroscopic Ground state: Term Symbol and LS coupling

(ii) When L =1 and S = 1

J = (L+S), (L+S-1), (L+S-2)……|L-S|
J = (1+1) (1+1-1) (1+1-2)
J = (2) (1) (0)
Complete spectroscopic Term symbol 2S+1L 3P 3P 3P
J 2, 1, 0
(ii) When L =0 and S = 1
J = (L+S), (L+S-1), (L+S-2)……|L-S|
J = (0+1)
J = (1)
Complete spectroscopic Term symbol 2S+1L 3S
J 1
(B) When L= 2, 1 and 0 and S = 0
L S Spectroscopic Term
2 0 1D
2

1 0 1P
1

0 0 1S
0
 Spectroscopic Ground state: Term Symbol
Calculation of Ground state term for p1, p2, p3, p4, p5 and p6 electrons.
1. p1 electron

a) L = 1 x1 = 1 for L= 1 the state will be ‘P’

b) spin multicity 2S+1 Where, S = n = number of unpaired electrons
+ 1 = 1+1 = 2
c) Calculation of LS coupling.
The only one unpaired electron present in p-orbital hence use L-S (Use L-S when
system contain half filled or less than half filled electron)
𝟏
J = L-S 1- = 𝟐 Hence ground state term 2S+1LJ will be 2P1/2
--------------------------------------------------------------------------------------------------------
2. p2 electrons

a) L = 1 x1 + 1 x 0 = 1 for L= 1 the state will be ‘P’

b) spin multicity 2S+1, 2x +1, 2x1+1 = 3
 Spectroscopic Ground state: Term Symbol
c) Calculation of LS coupling.
The two unpaired electron present in p-orbital hence use L-S
J = L-S 1- = 0 Hence ground state term 2S+1LJ will be 3P0
----------------------------------------------------------------------------------------------------
3. p3 electrons

a) L = 1+0-1 = 0 for L= 0 the state will be ‘S’

b) spin multicity 2S+1 Where, S = n = number of unpaired electrons
+ 1 = 3+1 = 4
c) Calculation of LS coupling.
The three unpaired electron present in p-orbital hence use L-S
J = L-S 0 - = 3/2 Hence ground state term 2S+1LJ will be 4S3/2
----------------------------------------------------------------------------------------------------
4. p4 electrons

a) L = 2+0-1 = 1 for L= 1 the state will be ‘P’

 Spectroscopic Ground state: Term Symbol

b) spin multicity 2S+1 Where, S = n = number of unpaired electrons

+ 1 = 2+1 = 3
c) Calculation of LS coupling.
The two unpaired electron with one paired electron present in p-orbital hence use L+S
(more than half filled)
J = L+S 1+ = 2 Hence ground state term 2S+1LJ will be 3P2
-------------------------------------------------------------------------------------------------------------
5. P5 electrons

a) L = 2+0-1 = 1 for L= 1 the state will be ‘P’

b) spin multicity 2S+1 Where, S = n = number of unpaired electrons

+1=2
c) Calculation of LS coupling.
The one unpaired electron with two paired electron present in p-orbital hence use L+S
(more than half filled)
J = L+S 1+ = 3/2 Hence ground state term 2S+1LJ will be 2P3/2
 Spectroscopic Ground state: Term Symbol
6. P6 electrons

a) L = 2+0-2 = 0 for L= 0 the state will be ‘S’

b) spin multicity 2S+1 Where, S = n = number of unpaired electrons

+1=1
c) Calculation of LS coupling.
The no unpaired electron present in p-orbital hence use L+S (more than half
filled)
J = L+S 1+ = 2/2 = 1 Hence ground state term 2S+1LJ will be 1S1
----------------------------------------------------------------------------------------------------
 Spectroscopic Ground state: Term Symbol
Calculation of Ground state term for d1, d2, d3, d4, d5, d6, d7, d8, d9, and d10
electrons.
1. d1 electron

a) L = 2 for L= 2 the state will be ‘D’

b) spin multicity 2S+1 Where, S = n = number of unpaired electrons

+1=2

c) Calculation of LS coupling.

The one unpaired electron present in d-orbital hence use L-S (for half
filled or less than half filled).

J = L-S 2- = 3/2 Hence ground state term 2S+1LJ will be 2D3/2

 Spectroscopic Ground state: Term Symbol
Calculation of Ground state term for d1, d2, d3, d4, d5, d6, d7, d8, d9, and d10
electrons.
2. d2 electrons

a) L = 2+1 for L= 3 the state will be ‘F’

b) spin multicity 2S+1 Where, S = n = number of unpaired electrons

+1=3

c) Calculation of LS coupling.

The two unpaired electron present in d-orbital hence use L-S (for half
filled or less than half filled).

J = L-S 3- = 2 Hence ground state term 2S+1LJ will be 3F2

 Spectroscopic Ground state: Term Symbol
Calculation of Ground state term for d1, d2, d3, d4, d5, d6, d7, d8, d9, and d10
electrons.
3. d3 electrons

a) L = 2+1+0 for L= 3 the state will be ‘F’

b) spin multicity 2S+1 Where, S = n = number of unpaired electrons

+1=4

c) Calculation of LS coupling.

The three unpaired electron present in d-orbital hence use L-S (for half
filled or less than half filled).

J = L-S 3- = 3/2 Hence ground state term 2S+1LJ will be 4F3/2

 Spectroscopic Ground state: Term Symbol
Calculation of Ground state term for d1, d2, d3, d4, d5, d6, d7, d8, d9, and d10
electrons.
4. d4 electrons

a) L = 2+1+0-1 for L= 2 the state will be ‘D’

b) spin multicity 2S+1 Where, S = n = number of unpaired electrons

+1=5

c) Calculation of LS coupling.

The four unpaired electron present in d-orbital hence use L-S (for half
filled or less than half filled).

J = L-S 2- = 0 Hence ground state term 2S+1LJ will be 5D0

 Spectroscopic Ground state: Term Symbol
Calculation of Ground state term for d1, d2, d3, d4, d5, d6, d7, d8, d9, and d10
electrons.
5. d5 electrons

a) L = 2+1+0-1-2 for L= 0 the state will be ‘S’

b) spin multicity 2S+1 Where, S = n = number of unpaired electrons

+1=6

c) Calculation of LS coupling.

The five unpaired electron present in d-orbital hence use L-S (for half
filled or less than half filled).

J = L-S 0- = 5/2 Hence ground state term 2S+1LJ will be 6S5/2

 Spectroscopic Ground state: Term Symbol
Calculation of Ground state term for d1, d2, d3, d4, d5, d6, d7, d8, d9, and d10
electrons.
6. d6 electrons

a) L = 4+1+0-1-2 for L= 2 the state will be ‘D’

b) spin multicity 2S+1 Where, S = n = number of unpaired electrons

+1=5

c) Calculation of LS coupling.

The four unpaired electrons with one paired electron present in d-orbital
hence use L+S (for more than half filled).

J = L+S 2+ = 4 Hence ground state term 2S+1LJ will be 5D4

 Spectroscopic Ground state: Term Symbol
Calculation of Ground state term for d1, d2, d3, d4, d5, d6, d7, d8, d9, and d10
electrons.
7. d7 electrons

a) L = 4+2+0-1-2 for L= 3 the state will be ‘F’

b) spin multicity 2S+1 Where, S = n = number of unpaired electrons

+1=4

c) Calculation of LS coupling.

The three unpaired electrons with two paired electrons present in d-orbital
hence use L+S (for more than half filled).

J = L+S 3+ = 9/2 Hence ground state term 2S+1LJ will be 3F9/2

 Spectroscopic Ground state: Term Symbol
Calculation of Ground state term for d1, d2, d3, d4, d5, d6, d7, d8, d9, and d10
electrons.
8. d8 electrons

a) L = 4+2+0-1-2 for L= 3 the state will be ‘F’

b) spin multicity 2S+1 Where, S = n = number of unpaired electrons

+1=3

c) Calculation of LS coupling.

The two unpaired electrons with three paired electrons present in d-orbital
hence use L+S (for more than half filled).

J = L+S 3+ = 4 Hence ground state term 2S+1LJ will be 3F4

 Spectroscopic Ground state: Term Symbol

Calculation of Ground state term for d1, d2, d3, d4, d5, d6, d7, d8, d9, and d10
electrons.
9. d9 electrons

a) L = 4+2+0-2-2 for L= 2 the state will be ‘D’

b) spin multicity 2S+1 Where, S = n = number of unpaired electrons

+1=2

c) Calculation of LS coupling.
The one unpaired electron with four paired electrons present in d-orbital
hence use L+S (for more than half filled).

J = L+S 2+ = 5/2 Hence ground state term 2S+1LJ will be 2D5/2

 Spectroscopic Ground state: Term Symbol

Calculation of Ground state term for d1, d2, d3, d4, d5, d6, d7, d8, d9, and d10
electrons.
10. d10 electrons

a) L = 4+2+0-2-4 for L= 0 the state will be ‘S’

b) spin multicity 2S+1 Where, S = n = number of unpaired electrons

+1=1

c) Calculation of LS coupling.
The no unpaired electron or all paired electrons present in d-orbital hence use
L+S (for more than half filled).

J = L+S 0+ = 0 Hence ground state term 2S+1LJ will be 1S0

 Selection rule for d-d transition

The main selection rule for electronic spectra are,

1. Transition in which there is change in the number of unpaired electrons in
going from a lower to a higher energy state are referred to as spin or
multiplicity forbidden. This means that transition to only those excited state
are to be considered which have the same spin multiplicity as ground state.
This is also given as ∆S = 0.
Example: for d2 configuration, that transition from 3F (ground state) to 3P
(excited state). The transition in which ∆S ≠ 0 (i.e. ∆S = ±1) are forbidden or
very weak.
2. For molecules having a Centre of symmetry, transitions which do not involve
a change in the subsidiary quantum number (∆ l = 0) are forbidden. These
forbidden transition are called Laporte forbidden transitions. For allowed
transition the ∆ l = ± 1.
Selection Rule Allowed Forbidden
∆S 0 ±1
∆l ±1 0
Orgel energy level diagram for d1 and d9 states
electronic spectrum of [Ti (H2O)6]3+ complex ion