The Electronic

Spectra of
Coordination
Compounds

Introduction
Many transition metal complexes are
colored. This is due to transitions of
electrons between the molecular
orbitals that are formed largely by the
d orbitals on the metal.
Many transitions are in the visible
range, with the color of the complex
taking on the complementary color of
the frequency or frequencies absorbed.

Introduction

General Features
Absorption bands in electronic
spectra are usually broad, and occur
much more rapidly than molecular
vibrations. As a result, the spectra
represent a snapshot of molecules
in various vibrational and rotational
states.

General Features
Extinction coefficients will range
from <1 up to 50,000 M-1cm-1
depending upon the type of
electronic transition and whether it
is permitted based on selection
rules.

Selection Rules
Electronic transitions obey the
following selection rules:
1. S = 0. Electrons cannot change
spin.
2. The Laporte rule states that there
must be a change in parity. Only
gu or ug transitions are allowed.
Thus, all dd transitions are
forbidden by this selection rule.

The
UV/Vis spectra
of transition
metal
complexes
show the
transitions of
the electrons.
Analysis
of these
spectra can be
quite complex.

Summary of
Observations-First Row
Transition Metal
Complexes (high spin)

d1, d4, d6 and d9 complexes show one

absorption.
d2, d3, d7 and d8 complexes show three
absorptions, with the 3rd peak often
obscured.
d5 complexes show very weak, sharp
absorptions.

Note that
even the
single peaks
show side
peaks or
overlapping
bands of
absorption.

Electron Spectra
The UV/Vis spectra are used to
determine the value of o for the
complex. The spectra arise from
electronic transitions between the t 2g and
eg sets of molecular orbitals. Electronelectron interactions can greatly
complicate the spectra. Only in the case
of a single electron is interpretation of
the spectrum straightforward.

Obtaining o
For a d1 configuration, only a single peak is
seen. It results from the electron promotion
from the t2g orbitals to the eg orbitals. The
toothed appearance of the peak is due to a
Jahn-Teller distortion of the excited state. The
energy of the peak = o.

General
Observations
d1, d4, d6 and d9
usually have 1
absorption, though
a side hump
results from JahnTeller distortions.

General
Observatio
ns

d2, d3, d7 and

d8 usually have 3
absorptions, one
is often
obscured by a
very intense
charge transfer
band.

General Observations
d5 complexes consist of very
weak, relatively sharp transitions
which are spin-forbidden, and have a
very low intensity.

Electronic Transitions
Absorption of light occurs when
electrons are promoted from lower
to higher energy states. Interactions
between electrons causes more than
one peak in the UV/Vis spectra of
these complexes. The electrons are
not independent of each other, and
the spin angular momenta and
orbital angular momenta interact.

Electronic Transitions
The interaction of orbital angular
momenta (ml values) and spin angular
momenta (ms values) is called RusselSaunders or LS coupling.
The lower transition metals (4d and
5d) undergo further coupling (called jj coupling or spin-orbit coupling).

3d Multi-electron
Complexes
The interactions produce atomic
states called microstates that are
described by a new set of quantum
numbers.
ML = total orbital angular
momentum =ml
MS = total spin angular
momentum = ms

Determining the Energy

States of an Atom
A microstate table that contains
all possible combinations of ml and
ms is constructed.
Each microstate represents a
possible electron configuration.
Both ground state and excited states
are considered.

Energy States
Microstates would have the same
energy only if repulsion between
electrons is negligible. In an
octahedral or tetrahedral complex,
microstates that correspond to
different relative spatial distributions
of the electrons will have different
energies. As a result, distinguishable
energy levels, called terms are seen.

Energy States
To obtain all of the terms for a
given electron configuration, a
microstate table is constructed. The
table is a grid of all possible
electronic arrangements. It lists all
of the possible values of spin and
orbital orientation. It includes both
ground and excited states, and must
obey the Pauli Exclusion Principle.

Constructing a
Microstate Table
Consider an atom of carbon. Its
highest occupied orbital has a p2
electron configuration.
Microstates correspond to the
various possible occupation of the px,
py and pz orbitals.

Constructing a
Microstate Table
ml = +1 0
Configurations:
___ ___ ___
___ ___ ___

-1 microstate:
___ ___ ___ (1+,0+)
(0+,-1+)
(1+,-1+)

These are examples of some of the

ground state microstates. Others
would have the electrons (arrows)
pointing down.

Constructing a
Microstate Table
ml = +1 0
Configurations:
___ ___ ___
___ ___ ___

-1 microstate:
___ ___ ___ (1+,1-)
(0+,0-)
(-1+,-1-)

These are examples of some of the

excited state microstates.

Microstate Table for p

For the carbon atom, ML will

range from +2 down to -2, and MS
can have values of +1 (both
electrons pointing up), 0 (one
electron up, one electron down),
or -1 (both electrons pointing
down).

Microstate Table for p

MS
ML

+1

+2:

1+1-

+1:

10

0:

-1+1+

-1:

-1+0+

-2:

+ +

1+0-
1-0+
-1+1-
0+0-
-1-1+
-1+0-
-1-0+
-1+-1-

-1

1-0-1-1-1-0-

The table
includes
all possible
microstate
s.

Constructing a
Microstate Table
Once the microstate table is
complete, the microstates are
collected or grouped into atomic
(coupled) energy states.

Constructing a
Microstate Table
For two electrons,
L = l1+ l2, l1+ l2-1, l1+ l2-2,l1- l2
For a p2 configuration, L = 1+1, 1+1-1,
1-1.
The values of L are: 2, 1 and 0.

L is always positive, and ranges from

the maximum value of l.

Constructing a
Microstate Table
For two electrons,
S = s1+ s2, s1+ s2-1, s1+ s2-2,s1- s2
For a p2 configuration, S = + ,
+ -1. The values of S are: 1
and 0.

Atomic Quantum
Numbers
Quantum numbers L and S
describe collections of microstates,
whereas ML and MS describe the
individual microstates themselves.

Constructing a
Microstate Table
The microstate table is a grid that
includes all possible combinations of
L, the total angular momentum
quantum number, and S, the total spin
angular momentum quantum number.
For two electrons,
L = l1+ l2, l1+ l2-1, l1+ l2-2,l1- l2
S = s1+ s2, s1+ s2-1, s1+ s2-2,s1- s2

Constructing a
Microstate Table
Once the microstate table is complete,
all microstates associated with an
energy state with specific value of L and
S are grouped.
It doesnt matter which specific
microstates are placed in the group.
Microstates are grouped and eliminated
until all microstates are associated with
a specific energy state or term.

Term Symbols
Each energy state or term is
represented by a term symbol. The
term symbol is a capitol letter that is
related to the value of L.
L=

Term
Symbol

Term Symbols
The upper left corner of the
term symbol contains a number
called the multiplicity. The
multiplicity is the number of
unpaired electrons +1, or 2S+1.

Microstate Table for p

MS
ML

+1

+2:

1+1-

+1:

10

0:

-1+1+

-1:

-1+0+

-2:

+ +

1+0-
1-0+
-1+1-
0+0-
-1-1+
-1+0-
-1-0+
-1+-1-

-1

1-0-1-1-1-0-

Eliminate
microstate
s with
ML=+22, with
Ms=0.

Microstate Table for p

MS
ML

+1

+2:

1+1-

+1:

10

0:

-1+1+

-1:

-1+0+

-2:

+ +

1+0-
1-0+
-1+1-
0+0-
-1-1+
-1+0-
-1-0+
-1+-1-

-1

1-0-1-1-1-0-

These
microstate
s are
associated
with the
term 1D.

Microstate Table for p

MS
ML

+1

+2:

1+1-

+1:

10

0:

-1+1+

-1:

-1+0+

-2:

+ +

1+0-
1-0+
-1+1-
0+0-
-1-1+
-1+0-
-1-0+
-1+-1-

-1

1-0-1-1-1-0-

Eliminate
microstate
s with
ML=+11, with
Ms=+1-1

Microstate Table for p

MS
ML

+1

+2:

1+1-

+1:

10

0:

-1+1+

-1:

-1+0+

-2:

+ +

1+0-
1-0+
-1+1-
0+0-
-1-1+
-1+0-
-1-0+
-1+-1-

-1

1-0-1-1-1-0-

Eliminate
microstate
s with
ML=+11, with
Ms=+1-1

Microstate Table for p

MS
ML

+1

+2:

1+1-

+1:

10

0:

-1+1+

-1:

-1+0+

-2:

+ +

1+0-
1-0+
-1+1-
0+0-
-1-1+
-1+0-
-1-0+
-1+-1-

-1

1-0-1-1-1-0-

These
microstate
s are
associated
with the
term 3P.

Microstate Table for p

MS
ML

+1

+2:

1+1-

+1:

10

0:

-1+1+

-1:

-1+0+

-2:

+ +

1+0-
1-0+
-1+1-
0+0-
-1-1+
-1+0-
-1-0+
-1+-1-

-1

1-0-1-1-1-0-

One
microstate
remains.
It is
associated
with the
term 1S.

Term States for p

The term states for a p2 electron

configuration are 1S, 3P, and 1D.
The term symbol with the
greatest multiplicity and highest
value of ML will be the ground state.
3P is the ground state term for
carbon.

Determining the Relative

Energy
of Term States

1. For a given electron configuration,

the term with the greatest
multiplicity lies lowest in energy.
(This is consistent with Hunds rule.)
2. For a term of a given multiplicity,
the greater the value of L, the lower
the energy.

Determining the Relative

Energy
of Term
States
2
For a p configuration, the
term states are 3P, 1D and 1S.
The terms for the free
atom should have the following
relative energies:
P< 1D <1S

Determining the Relative

Energy
of Term States
The rules for predicting the
ground state always work, but
they may fail in predicting the
order of energies for excited
states.

Energy States for a d2

Configuration
A microstate table for a d2
electron configuration will contain
45 microstates (ML = 4-4, and
MS=1, 0 or -1) associated with the
following terms:
1S, 1D, 1G, 3P, and 3F

Energy States for a d2

Configuration

Problem: Determine the ground

state of a free atom with a d2
electron configuration, and place the
terms in order of increasing energy.
S, 1D, 1G, 3P, and 3F

Determining the Ground

State Term
We only need to know the ground state
term to interpret the spectra of
transition metal complexes. This can be
obtained without constructing a
microstate table.
The ground state will
a) have the maximum multiplicity
b) have the maximum value of ML for the
configuration obtained in part (a).