Coordination Chemistry III:

Electronic Spectra
Chapter 11
Coordination Complexes
Unlike most organic compounds, many
coordination compounds have vivid colors.
These vivid colors are due to the electronic
transitions between the d-orbitals of the metal.
The energy levels of d electron
configurations, however, are usually more
complicated than might be expected since
the electrons in the atomic orbitals interact
with each other.
Absorption of Light
Complementary colors if a compound
absorbed light of one color, the complement of
that color is observed.
[Cu(H
2
O)
6
]
2+
has a blue color. What is absorbed?
Beer-Lambert Absorption Law
log(I
o
/I)=A=lc (define variables)
In a common absorption spectrum, the A is plotted versus
wavelength or cm
-1
(1/).
Quantum Numbers of
Multielectron Atoms
In order to understand energy transitions between states
with more than one electron, we need to understand in
more detail how these electrons interact with each other.
Each conceivable set of individual m
l
and m
s
values
constitutes a microstate of the configuration.
How many microstates in a d
1
configuration?
Examine the carbon atom (p
2
configuration)
Determine the electron configuration and quantum numbers.
Independently, each of the 2p electrons could have one of six possible
combinations. The two electrons, however, are not independent of each
other.
Interaction between Electrons
In any microstate, the individual orbital magnetic
moments (related to m
l
) and the spin magnetic moments
(related to m
s
) will interact resulting in an energy state or
term for the configuration.
Commonly, a number of microstates will contribute to a single
term (degeneracies).
This is an approximation using the one-electron wave
mechanical mode.
Works well for 1
st
and 2
nd
row transition metals.
Term Designation (Free-Ion)

2S+1
L
L and S relate to the overall orbital and spin angular
momenta for the system (or state).
L = overall orbital angular momentum quantum
number.
Discuss possible values (analogous to the l quantum
number).
L is related to the vectorial addition of vectors taken from
the l quantum number.
Discuss the permitted ways in which the l values can
combine (Figure 20, Carter).
Overall Orbital Angular
Momentum Quantum Number, L
The vectorial addition produces the possible terms for a
given configuration.
For a given term, the magnitude of the resultant angular
momentum is fixed, [L(L+1)]
1/2
(h/2).
The vector for the momentum can have a number of
allowed orientations.
A partial lift of degeneracy by the magnetic field.
Allowed orientations for a given term are associated with the
overall magnetic quantum number, M
L
.
M
L
= L, L-1,.-L
Overall Orbital Angular
Momentum Quantum Number, L
M
L
relates to the orbital multiplicity or orbital
degeneracy (Each has projection equal in magnitude
to M
L
(h/2)).
What are the allowed orientations for a D term?
In the Russell-Saunders scheme, M
L
= m
l
.
An M
L
value can be assigned to each microstate.
Therefore, a given L value must arise from a complete
set of microstates with the 2L+1 values.
Examples
Overall Spin Quantum Number, S
Spin state of the term.
2S+1 spin multiplicity of the state.
S=0, 1, 2
Like L, S can be obtained by vectorial addition of the
spin angular momentum vectors (related to s or m
s
).
Magnitude [S(S+1)]
1/2
(h/2)
S is related to an overall spin quantum number, M
S
.
M
S
= S, S-1,-S (2S+1 values)
Indicates the allowed orientations of the vector relative to an
applied magnetic field. The produces the spin degeneracy in a
spin state.
Overall Spin Quantum Number, S
Magnitude of the spin angular momentum is
[S(S+1)]
1/2
(h/2), but its projections on a
particular axis in the allowed orientation are
given by M
S
(h/2).
Russell-Saunders scheme, M
S
=m
s
In Summary
Any given term with L and S values arises from
a set of microstates that has the necessary 2L+1
values of M
L
and also the necessary 2S+1
values of M
S
.

Value of the term
L = largest possible value of M
L
Lets do the d
2
configuration.
Determining Microstates
Determine the number of microstates for a triplet P.
What are the allowed M
L
and M
S
values?
Determine the number of microstates for a doublet D.
What are the allowed M
L
and M
S
values?
It is sufficient to designate the microstates by x (only the
number is important).
Number of microstates in a given free-ion term is
equal to (2L + 1)(2S +1).
Row multiplied by column
Reducing a Microstate Table/Configuration
into Its Free-Ion Terms
Notice that each term is composed of a rectangular
array of microstates.
This process is shown for a p
2
configuration in Table
11-4.
The spin multiplicity is same as the number of columns
of microstates.
The # of rows to include in the rectangular array is
equal to +L -L (number of values).
(2L+1)(2S+1)
Do the p
2
and d
2
configurations.
Term of the Lowest Energy
The ground term (lowest energy) has the highest
spin multiplicity.
If two or more terms share the same maximum
spin multiplicity, the ground term is the one
having the highest L value.
What is the term with the lowest energy for the d
2

configuration?
Spin-Orbit Coupling
There is also spin-orbit coupling wherein the
spin and orbital angular momenta couple with
each other.
J = L+S, L+S-1, L+S-2,.L-S| (no negative values)
J is a subscript on the right side of the L quantum #
Determine the spin-orbit coupling in the
1
S and
3
P
free-ion terms. Designate these with J.
Page 388
Lowest Energy Term Including
Spin-Orbit Coupling
For subshells (such as p
2
) that are less than
half-filled, the state having the lowest J value
has the lowest energy. For subshells that are
more than half-filled, the state having the
highest J value has the lowest energy.
Determine the lowest energy state for the p
2

configuration.
Electronic Spectra of
Coordination Compounds
Absorption spectra in most cases involve the d orbitals
of the metal.
Identifying lowest energy term (quickly)
Sketch the energy levels showing the d electrons.
Spin multiplicity of lowest-energy state equal highest
possible number of unpaired electrons +1.
Determine the maximum possible value of M
L
(m
s
) for the
configuration.
Combine steps.
High- and low-spin d
6
configurations in octahedral symmetry.
Reducing the Symmetry of the
Free Ion by a Ligand Field
The orbital term symbols for the free
atom/ion are identical to the symbols for the
appropriate symmetry species in the
spherical group, R
3
(show Table).
There are no inherent symmetry restrictions on
possible orbital degeneracies.
D fivefold degeneracy (M
L
= ?)
F ???
Correlation Table
Reducing the Symmetry of the
Free Ion by a Ligand Field
When a ligand field is imposed, however, there are
restrictions placed on the maximum orbital degeneracy.
In an octahedral complex, the maximum degeneracy is 3 (T-
type IRs, look at table). Orbital degeneracies present in the
free ion must be split.
All term symbols will be redefined by the new
symmetry.
Upon reducing the symmetry, the free-ion term can be
treated as a reducible representation composed of
irreducible representations in the appropriate character
table.
Reducing the Symmetry of the
Free Ion by a Ligand Field
The total number of microstates, D
t
, remains the
same.
Do the d
1
configuration.
What does this split into when an octahedral field is
imposed?
How many microstates are possible when imposing the
ligand field?
The new ligand-field terms will retain the original spin
multiplicities found in the free-ion terms.
Examine
Correlation Diagrams Relating Electron
Spectra to Ligand Field Splitting
Examine the correlation diagram for a d
2
configuration
in an octahedral ligand field.
Far left (absence of ligand field) the free-ion terms. On this
side, the ligand field has very little influence.
Examine the previous table.
Far right (strong ligand field) the states are largely
determined by the ligand field.
Observed before in the crystal field and ligand field discussion.
In real compounds, the situation is somewhere in the
middle.
Splitting of Free-Ion Terms
Irreducible representations are produced.
Examine the correlation diagram and the O
h
table.
Table 11-6
Each state has symmetric characteristics of that IR.
IRs are also obtained from the strong-field limit
configurations (right side of table).
The IRs on the right and left sides must
correlate.
Selection Rules for Transitions
Transitions between states of the same
parity are forbidden.
Laporte Selection Rule
Transitions between states of different spin
multiplicities are forbidden.

4
A
2

4
T
1
and
4
A
2

2
A
2
Discuss how the rules are relaxed on the expected
absorption intensities.
Tanabe-Sugano Diagrams
Special correlation diagrams useful in the interpretation
of electronic spectra.
Lowest energy state is plotted along the horizontal axis.

o
/B (field strength)
Vertical axis is the measure of the energy above the ground
state
E/B
B = Racah parameter, a measure of the repulsion between terms of the
same multiplicity.
Lines connecting states of the same symmetry cannot cross.
A d
2
Configuration, [V(H
2
O)
6
]
3+
Electron Configurations
The diagrams of d
2
-d
8
are illustrated in Figure 11-7.
There is a vertical line near the center of d
4
-d
7
diagrams.
What does the vertical line represent? What happens
once the line is crossed?
In some cases, the absorption bands are off-scale (x-axis)
or obscured by the charge-transfer bands (discussed
later).
Discuss the terms for the configurations. They are not
the same as observed for the orbital terms.
Jahn-Teller Distortions
Spectrum of the [Ti(H
2
O)
6
]
3+
complex.
The complex has a d
1
configuration (Fig. 11-8).
Go over terms for the configurations.
Why are there two overlapping bands?
If degenerate orbitals are asymmetrically occupied a distortion will
occur to remove the degeneracy.
Jahn-Teller distortion is usually only significant for
asymmetrically occupied e
g
orbitals.
The others cannot be resolved.
The most common distortion is along the z-axis (elongation).
Symmetry Labels for Configurations
Symmetry labels for electron configurations
match their degeneracies.
T = triply degenerate asymmetrical state
E = doubly degenerate asymmetrical state
A or B = nondegenerate
Do a few without Jahn Teller splitting/distortion.
Effect of a D
4h
field.