Electronic Spectra of Transition Metal

Electronic Spectra of
Transition Metal
Complexes
Dr. Gurpreet Kaur
Assistant Professor
PGGCG-42
Chandigarh
Basis of Electron Absorption Spectroscopy
 Transition Metal (TM) compounds appear coloured because they absorb light of
particular wavelength of frequency in the visible region. The colour given by the
compound is complimentary to the colour of light absorbed.
The extent of intensity of absorption of light of a particular wavelength or a
frequency can be obtained by Beer-Lambert Law explained as follows:-
Term Symbols & LS Coupling
 Term symbol is an abbreviated description of the (total)
angular momentum quantum numbers in a multi-electron atom, however, even a
single electron can be described by a term symbol. Each energy level of an atom
with a given electron configuration is described by not only the electron
configuration but also its own term symbol, as the energy level also depends on
the total angular momentum including spin. The usual atomic term symbols
assume LS coupling (also known as Russell–Saunders coupling or spin–orbit
coupling). The ground state term symbol is predicted by Hund's rules.
 For light atoms, the spin–orbit interaction (or coupling) is small so that the total
orbital angular momentum L and total spin S are good quantum numbers. The
interaction between L and S is known as LS coupling, Russell–Saunders
coupling (named after Henry Norris Russell and Frederick Albert Saunders, who
described this in 1925) or spin–orbit coupling. Atomic states are then well
described by term symbols of the form
Derivation of Term Symbols for p2 Configuration
All the spectroscopic terms derived for p2 configuration would occur for an excited state of carbon
(1s2 2s2 2p2) in which two p electrons belongs to different subshells.
Steps to assign spectroscopic term symbol
Derivation of Term Symbols for d2 Configuration
For d electrons, the subsidiary quantum number l =2.
For two d-electrons having l1 = 1 and l2 = 2,
L = 4, 3, 2, 1, 0
S = 1, 0
2S + 1 =3 and 1
There are 45 ways in which two d electrons may be
arranged which do not violate the Pauli Exclusion
Principle. These arrangements are shown in a table
Calculation of Number of Microstates
The number of microstates possible for any electronic configuration may be calculated from the
formula:-
Number of microstates = n! / r! (n - r)!
Where n is the twice the number of orbitals,

r is the number of electrons
! is the factorial.
For p2 configuration,
n= 3x2 =6; r = 2; n – r = 4; 6! = 6 x 5 x 4 x 3 x 2 x 1 = 720; 2! = 2 x 1 =2; 4! = 4 x 3 x 2 x 1 = 24
Substituting in the formula, we get
Number of microstates =15.
Similarly, for a d2 configuration,
Number of microstates = 10! / 2! (10 – 2)!
Thus a d2 configuration will have 45 microstates.
Selection Rules
1. Spin selection rule
The selection Rule for Spin Angular Momentum is
ΔS=0
Thus transitions such as 2S→ 2P and 3D→ 3P are allowed,
but transition such as 1S→ 3P is forbidden.
The same rule is also stated in the form of a statement,
Electronic Transitions between the different states of spin multiplicity are
forbidden.
The selection Rule for total angular momentum, J, is
Δ J = 0 or ± 1
The transitions such as 2P1/2 → 2D3/2 and 2P3/2 → 2D3/2 are allowed, but
transition such as
2
P1/2 → 2D5/2 is forbidden since Δ J= 2.
There is no selection rule governing the change in the value of n, the
principal quantum
number..
2. Laporte selection rule: Also known as orbital selection rule. This rule states that
transitions between the orbitals of the same sub shell are forbidden. In other words,
For total orbital angular momentum is Δ L = ± 1. This is La Porte allowed transitions.
Thus transition such as 1S→ 1P and 2D→ 2P are allowed
But transition such as 3D→ 3S is forbidden since Δ L = -2 .
Hence transitions from gerade to ungerade (g to u) or vice versa are allowed, i.e., u → g
or g → u but not u → u or g → g.
In the case of p sub shell, both ground and excited states are odd and in the case of d sub
shell both ground and excited states are even. As a rule transition should be from even to
odd or vice versa. T
he same rule is also stated in the form of a statement instead of an equation: Electronic
transitions within the same p or d sub-shell are forbidden, if the molecule has centre of
symmetry.
According to Laporte selection rule, d-d transitions of octahedral
complexes are forbidden. Then why moderately strong spectra actually
observed?
Splitting of Russell Saunders states in octahedral and tetrahedral states
 The symbols A(or a) and B (or b) with any suffixes indicate wave functions which are singly degenerate. Similarly E
(or e) indicates double degeneracy and T (or t) indicates triple degeneracy.
 Lower case symbols, a1g, a2g, eg, etc., are used to indicate electron wave functions(orbitals) and upper case symbols
are used to describe electronic energy levels. Thus 2T2g means an energy level which is triply degenerate with respect
to orbital state and also doubly degenerate with respect to its spin state.
 Upper case symbols are also used without any spin multiplicity term and they then refer to symmetry (ex., A1g
symmetry). The subscripts g and u indicate gerade (even) and ungerade (odd).
 d orbitals split into two sets - t2g orbitals and eg orbitals under the influence crystal field.
 f orbitals split into three sets, having symmetries A2u, T2u and T1u.
In an Octahedral field Thus states split by external field are called Mulliken
 S and P states do not split Symbols. These symbols are extensively used in
interpreting electronic spectra of TM complexes.
 D state split into two states
 F state split into three states
 G state split into four states
Spectrochemical Series for Ligands
NATURE OF ELECTRONIC
TRANSITONS & SPECTRA OF TM
COMPLEXES:
ORGEL ENERGY LEVEL DIAGRAMS
Spectra of d1 and d9 ions
Octahedral Complexes of Metal ion with d1 configuration
Octahedral Complexes of Metal ion with d9 configuration
Octahedral Complexes of Metal ions with d8 configuration

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Electronic Spectra of

Number of microstates = n! / r! (n - r)!

Where n is the twice the number of orbitals,

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