ELECTRONIC

SPECTRA OF
COMPLEXES
ITU Chemistry Department
2019/20 Spring Semester
The band at lowest energy is very weak that is an example of a spin-
fordidden transition.The two bands with intermediate intensities, which
will turn out to be spin allowed transitions between the t2g and eg
orbitals of the comp (t22ge1g  t32g), which are derived from the
metal d orbitals. The third feature in the spectrum is the intense band
at short wavelenth labeled CT which is related with charge-transfer.
This splitting of a single transition into two bands is in fact an outcome
of the electron-electron repulsions that will be one focus of this
chapter.
The electronic spectra of atoms

The different ways in which can occupy the orbitals specified

in the configuration are called the microstates of the configura
tion. For example, one microstate of a 2p2 configuration is
(1+, 1-); this notation signifies that both electrons occupy an
orbital with ml = +1 but do so opposite spins, the superscript
+ indicating ms = +1/2 and – indicating ms = +1/2. Another
microstate of the same configuration is (-1+, 0+). In this
microstate, both electrons have ms = +1/2 but one occupies
the 2p orbital with ml = -1 and the other occupies the orbital
with ml = 0
Spectroscopic Term

If we group together the microstates that have same energy when

electron repulsion are taken into account, we obtain the spectros-
copically distinguishable energy levels called terms.
The most important property of a microstate for helping us to
decide its energy is the relative orientation of the spins of the
electrons. Next in important is the relative orientation of the
orbital angular momenta of the electrons. It follows that we can
identify the terms of ligth atoms and put them in order of energy
by sorting the microstate to their total spin quantum number S
and then according to their total orbital angular momentum
quantum number L.
By analogy with the notation s,p,d,..... For orbitals l = 0,1,2,.....
the orbital angular momentum of an atomic term is denoted
by the equivalent upper case letter,

L= 0 1 2 3 4 ......
S P D F G then alphabetical

ML= ml1+ ml2

MS = ms1+ms2
The total spin is normally reported as the value of 2S+1, which
is called the multiplicity of the term:
S= 0 ½ 1 3/2 2 ............
2S+1 1 2 3 4 5 ............
The multiplicity is written as a left superscript on the letter
representing the value of L, and the entire label of a term
is called a term symbol.Thus, the term symbol 3P denotes
a term (a collection of degenerate state) with L= 1 and S= 1
and is called “triplet” term.
Example: Give the term symbols for an atom with the configurations
(a) s1, (b) p1, and (c ) s1p1.
Answer: (a) The single s electron has l = 0 and s = ½. Because there
is only one electron, L= 0 (an S term), S= ½, and 2S+1= 2(a doublet
Term).The term symbol is therefore 2S. (b) For a single p electron,
l= 1 so L= 1 and the term is 2P.(c) With one s and p electron, L=0+1=1,
a P term. The electrons may be paired (S=0) or (S=1). Hence both
1P and 3P terms are possible.

Self-test What terms arise from a p1d1 configuration?

The classification of microstates
We start the analysis by setting up a table of microstates of the d2
configuration;have been only the microstates allowed by the pauli
principle have been included.The largest value of ML, which for a
d2 configuration is +4. This state must belong to a term with L=4
(a G term).
We can concluded that the terms of a 3d2 configuration are
1G, 3F, 1D, 3P, and 1S. These terms account for all 45 permitted

states

Term Number of state

1G 9x1 = 9
3F 7x3 = 21
1D 5x1 = 5
3P 3x3 = 9
1S 1x1 = 1
Total: 45
The energies of the term
It is possible to identify the term of lowest energy by using Hund’s rule
1. For a given configuration, the term with the greatest multiplicity lies
lowest in energy. For the d2 configuration, this rule predicts that the
ground state will be either 3F or 3P.
2. For a term of given multiplicity, the greater value of L, the lower the
energy. In this case, the 3F term is lower in energy than 3P term.The
ground term of a d2 species such as Ti2+ is expected to be 3F.
Thus, for d2 the rules predict the order

3F 3P  1G  1D  1S

but the order observed for Ti2+ from spectroscopy is

3F  1D  3P  1G  1S
The procedure may then be summarized as follows:

1. Identify the microstate that has the highest value of Ms

2. Identify the highest value of ML for that multiplicity

Example: What is the ground term for the configurations

a) 3d5 of Mn2+ and b) 3d3 of Cr3+?
Answer a) The d5 configuration permits occupation of each d orbital
singly, the maximum value of S is 5/2 and the maximum multiplicity
is 2x5/2+1 = 6, a sextet term, L =0 and the term 6S. B) For the
configuration d3, the maximum multiplicity corresponds to all three
electrons having the same spin quantum number,so S= 3/2. The
multiplicity is 2 x3/2 + 1= 4, quartet. ML = 2+1+0 =3, an F term.
The ground term of d3 is 4F.
Selection rule
The relative intensities of absorption bands are governed by a series
of selection rules which are based on the symmetry and spin multip-
licity of ground and exited electronic state
1. Transitions between states of the same parity (symmetry with res-
respect to a center of inversion) are forbidden.This means that tran-
sitions between d orbitals are forbidden (g  g) transitions;(d orbitals
are symmetric to inversion),but transition between d and p orbitals
are allowed(g  u);p orbitals antisymmetric to inversion. This is
known as the Laporte selection rule.
2. Transition between states of different spin multiplicities are forbidden.
For example, transition between 4A2 and 4T1 are spin-allowed,but
between 4A2 and 2A2 are spin-forbidden.
These rules would seem to rule out most electronic transition for tran-
sition metal complexes by various mechanism in which these rules
can be relaxed.
Some of the most important of these mechanism:

1. The bonds in transition metal complexes are not rigid but undergo
vibrations that may temporarily change the symmetry which provides
a way to relax the first selection rule.As a consequence, d-d transitions
having molar absorptivities in the range of approximately 10 to 50
L mol-1 cm-1 commomly occur.
2. Tetrahedral complexes often absorb more srongly than octahedral
complexes of the same metal in the same oxidation state.The mixing
of p orbital character (of u symmetry) with d orbital character provides
a second way of relaxing the first selection rule.
3. Spin-orbital coupling in some cases provides a mechanism of relaxa-
tion of the second selection rule. Such absoption bands are usually
very weak, with typical molar absorptivities less than 1 L mol-1 cm-1.
Our first example will be a metal complex having a d2 configuration
and octahedral geometry: [V(H2O)]3+.
In discussing spectra, it will be particularly useful to be able to relate
the electronic spectra of transition metal complexes to the ligand-
field splitting, o for octahedral complexes.To do this, it will be necas-
cary to introduce two special types of diagrams, correlation diagram
and Tanabe-Sugano diagrams.
Correlation Diagrams (Orgel Diagrams)
These diagrams make use of two extremes:
1 Free ions (no ligand field): d2 configuration has 3F,3P,1G,1D, and 1S
terms, with the 3F term being of lowest energy.These term describe
the eneryg levels of a free d2 ion in the absence of any interaction
with ligands.These free ion terms will be shown on the far left.
 2 Strong Field Ligand
There are three possible configurations for two d electrons in an octa-
hedral ligand field.

In correlation diagrams, we will show these states on the far right, as the
srong field limit
In actual coordination comp, the situation is intermediate between these
extremes.For d2, the five terms 3F,3P,1G,1D, and 1S; these terms will
represent five different atomic states having different energies.The ef-
fect of ligands tend to push the energy levels toward t22g, t12ge1g, and
e2g configurations.In constructing a diagram to correlate the free ion
and srong field limits, we will seek a way to deal with the in-between
case in which both factors are important.
In an octahedral ligand field the free ion terms will be split into
states corresponding to the irreducible representations as shown
Below.

Splitting of free ion terms in octahedral symmetry

Although representations based on atomic orbitals may have either
g or u symmetry, the terms given here are d orbitals and as a result
have only g symmetry.
Correlation diagram for
a free ion and the srong-
field terms of a d2 confg.
From the information of The cystal-field theory

E(t22g, T1g) = 2(-2/5o) = -0.8 o

E(t12ge1g, T2g) = (-2/5+ -3/5) o = +0.2 o
E(e2g, A2g) = 2(3/5) o = +1.2 o

Therefore, relative to the energy of the lowest term, their energy are
E(t22g, T1g) =0 ; E(t12ge1g, T2g) = + o ; E(e2g, A2g) = +2 o

In summary, For a given metal ion, the energy of the individual terms
respond differently to ligands of incresing field strength and the
correlation between free atom terms of a complex can be displayed
on an Orgel diagram.
Tanabe-Sugano diagrams
These diagrams are special correlation diagrams that are particularly
useful in the interpretation of electronic spectra of coordination
comps.The lowest energy state is plotted along the horizontal axis,thus
the vertical distance above this axis is a measure of the energy above
the ground state. This diagrams depict the energy of electronic
states of comp. As a function of the
srength of the ligand field.
the horizontal axis: o/B
B= Racah parameter, a measure of repulsion
between terms of the same multiplicity. For
d2, the energy difference between 3F and 3P
is 15B.
Vertical axis: E/B where E is the energy abo-
ve the ground state.

Tanabe-Sugano diagram for d2 confg.

 Absorption spectrum of [V(H2O)6]3+

Spin-allowed transitions for Two bands are readily observed at

17800 and 25000 cm-1, a third band
d2 confg.
,at approximately 38000cm-1 , is obs-
cured in solution by charge transfer
bands nearby.
Electronic spectrum of [Cr(H2O)6]3+

1 4A2g(F)  4T2g
2 4A2g(F)  4T1g(F)
3 4A2g(F)  4T1g(P)
Electronic spectrum of [Cr(H2O)6]2+
1 5Eg(D)  5T2g
Electronic spectrum of [Mn(H2O)6]2+
Why is absorption by [Mn(H2O)6]2+
so weak?
6A Excited states is no spin-allo-
1
wed absoption, may be very weak
forbidden transitions to excited state
of spin multiplicity other than 6
Electronic spectrum of [Fe(H2O)6]2+

1 5T2g(D)  5Eg
Electronic spectrum of [Co(H2O)6]2+
1 4T1g(F)  4T2g
2 4T1g(F)  4A2g
1 4T1g(F)  4T1g (P)
Electronic spectrum of [Ni(H2O)6]2+

1 3A2g(F)  3T2g
2 3A2g(F)  3T1g
3 3A2g(F)  3T1g (P)
 B1g Eg

B1g B2g

When degenerate orbitals are asymmet

rically occupied, J-T distortions are
likely

Free ion term Oh D4h

Eg  A1g
Eg  B1g
Applications of Tanabe-Sugano Diagrams:
Determining o from spectra
o can be determined depend on the d electron configuration of the
Metal
d1, d4(high spin), d6(high spin), d9
d1 d4(high spin) d6 (high spin) d9

Determining o for d1, d4(h.s.), d6 (h.s.), and d9 confg.

d2 (or d7 confg.) d3(or d8 confg.)
 1 3T1g(F)  3T2g
2 3T1g(F)  3T1g(P)
3 3T1g(F)  3A2g

o = the energy difference between 3A2g

And 3T2g
o= [Energy of transition 3T1g 3A2g] –
[Energy of transition 3T1g  3T2g]
Example: [V(H2O)6]3+ has absorption at 17800 and 25700 cm-1.
Using Tanabe-Sugano diagram for d2, estimate values of o and B
for this complex.

From the Tanabe-Sugano diagram there are three possible spin-

allowed transitios:
1 3T1g(F)  3T2g (lowest energy)
2 3T1g(F)  3T1g(P)
3 3T1g(F)  3A2g
The ratio of energies of the absorption bands,
25700/17800 = 1.44
The ratio of energy of the higher energy transition(2 or 3) to the lowest
energy transition () must be approximately 1.44. FromT-S diagrams,
we can see that the ratio of 3 to 1 is approximately 2,regardless of the
srength of ligand field thereby eliminating 3 . This means that the
25700 band must be 2 for 2 3T1g(F)  3T1g(P).
1.44 = 2/ 1
The ratio varies as a function of the strength of the ligand field.By
taking values from Fig. And plotting the ratio 2/ 1 versus o/B
We find that 2/ 1= 1.44 approximately o/B= 31
2: E/B = 42(approximately): B= E/42 = 25700cm-1/42 = 610 cm-1
1. E/B = 29 (approximately): B= E/29 = 17800 cm-1/29= 610 cm-1
Since o/B= 31, o= 31xB = 31x 610 cm-1 = 19000cm-1
The nephelauxetic series
In the same example, we found that B = 610 cm-1 for [V(H2O)6]3+.
This value is smaller than that of a free ion in the gas phase(B= 861 cm-1),
which indicates that electron repulsions are weaker than in the free
ion. This weakening occurs because the occupied moleculer orbitals
are delocalized over the ligands and away from the metal.
The reduction of B from its free ion values is normally reported in
terms of the nephelauxetic parameter,:

= B(comp)/ B(free ion)

The values of  depend on the metal ion and the ligand. They vary
along the nephelauxetic series:

Br- Cl-  CN-  NH3  H2O  F-

A small value of  indicates a large measure of d-electron delocalization
on to the ligands and hence a significant character in the complex.The
softer ligand, the smaller the nephelauxetic parameter.
 [Ni(en)3]2+(purple) Each spectrum has three
2+ bands as expected d8 octa-
[Ni(H2O)6] (green)
hedral comp. [Ni(en)3]2+
bands are at higher frequen-
cies than corresponding
25000cm-1 [Ni(H2O)6]2+bands, in accord
14000cm-1 9000cm-1 with the spectrochemical
Series. On the basis of
the Orgel and Tanabe-
Sugano diagrams,One would
Absorption spectra of [Ni(H2O)6]2+ assign the lowest frquency
band to 3A2g3T1g(F) tran-
2+
(solid line,) and [Ni(en)3] (dashed
line).The colors of the visible region sition,the intermediate-
frequency band to 3A2g
of the spectrum are indicated above.
3T2g(F) and highest one to
o for [Ni(H2O)6]2+ is 9000 cm-1 3A2g3T1g(P).The possi-
Which is the lowest transition bility can be verified by using
Energy. the d8 T-S diagrams