G - Tanabe-Sugano diagrams.

A Tanabe-Sugano diagram is a special type of correlation diagram

that is particularly useful for the interpretation of electronic spectra for
transition metal complexes. In a Tanabe-Sugano diagram, the ground
state term is set as the base line and all other energies are
referenced to this ground state. The energy and Do are presented as
multiples of the principal Racah parameter B, and energies are
calculated using a value of C (~ 4) which is reported in the diagram.

It is fortunate that we do not need to carry out detailed analysis for

all cases. The Tanabe-Sugano diagrams have been worked out for
most dn configurations with common geometries (e.g. octahedral and
tetrahedral). Tanabe-Sugano diagrams for octahedral complexes are
shown below.
Tanabe-Sugano Diagrams for Octahedral dn Complexes
Tetrahedral Complexes
The same octahedral Tanabe-Sugano diagrams can be used for
tetrahedral complexes. However, for a dn tetrahedral complex, the
d(10-n) Tanabe-Sugano diagram must be used (i.e. for d8 Td, use the d2
Oh T-S diagram). For more details, see Miessler and Tarr, Inorganic
Chemistry, 3rd Edition, pg 406.
Some important general observations from the Tanabe-Sugano
diagrams are:

(1) Some lines are curved. This arises because whenever two states
of the same symmetry (same term symbol) are close in energy, they
can be combined to yield one state of lower energy and another of
higher energy. In a Tanabe-Sugano diagram, this makes it appear that
some lines bend away from each other to avoid crossing. As a result,
this phenomenon is referred to as the non-crossing rule. Note that
transitions involving these curved lines must be avoided when
determining Do from Tanabe-Sugano diagrams.

(2) For some configurations, there is an abrupt change of slope and

the ground state term also changes. This happens when there is a
transition from a High-Spin to a Low-Spin state.
What can we do with Tanabe-Sugano
Diagrams?
Qualitative Information:
Prediction of the number of observed transitions.

e.g. How many spin allowed transitions would be

expected for [Cr(OH2)3]3+

d3 - Ground State: 4A2

Spin Allowed transitions:

4T 4A
2 2
4T 4A
1 2
4T 4A
1 2

High or low spin?

e.g. How many spin allowed transitions would be

expected for Fe3+

d5 If high spin, then ground state: 6A1

No Spin Allowed transitions.

If low spin, then ground state: 2T2

Spin Allowed transitions:

2A 2T
2 2
2T 2T
1 2
2E 2T
2
2A 2T
1 2
Quantitative Information:
Calculation off Do and Racah Parameter B.

e.g. Deduce the values of Do and B for [Cr(NH3)6]3+

from the following spectrum and a TS diagram.
d3 - Ground State: 4A2

Spin Allowed transitions:

4T 4A
2 2
4T 4A
1 2
4T 4A
1 2

2 low energy transitions:

21550 cm-1 and 28500 cm-1
Where on the continuum of Do magnitude does this
complex lie? (i.e. How large is Do?)

If we look at the ratio of the energies for the two

observed transitions we see that 28500/21550 = 1.32.
Where on the TS diagram do we see this ratio of
energies for the two transitions?

-At Do/B = 33
On the vertical axis E/B = 32.8 (for the first transition)

Hence:
E/B = Do/B
21550 cm-1/32.8B = Do/33B
Do(32.8B) = 21550 cm-1(33B)
32.8 Do = 711150 cm-1
Do = 21681 cm-1

E/B = 32.8
21550 cm-1/B = 32.8
B = 657 cm-1
Another Example of a Quantitative Question:

A Chem 3840 student, whom well call Paul,

attempted to prepare Na2PdI4 in the laboratory. In
an effort to confirm the identity of the dark solid,
he obtained the UV-Visible spectrum which
exhibited 2 peaks. Unfortunately, over lunch Paul
spilled his drink on the spectrum, completely
obliterating the low energy peak. Due to poor
management he had not saved the spectrum
electronically, and had discarded the product.
After careful analysis of the soiled spectrum,
however, he determined that the energy for the
second transition was 31,980 cm-1. Upon
consulting the literature he found two conflicting
values for both the energy of the first transition
(23,400 and 27,640 cm-1) and B (590 and 780
cm-1).

a) What are the correct values of E and B?

b) Why are only 2 absorptions observed?
a) d8 - Ground State: 3A2

Spin Allowed transitions:

3T 3A
2 2
3T 3A
1 2
3T 3A (very high in energy)
1 2

With the available information, we have two possible

ratios for energies of transitions:

31980 cm-1/23400 cm-1 = 1.37

31980 cm-1/27640 cm-1 = 1.15

The correct value of E/B has to equal one of these ratios.

Given the available information, there are 4 possibilities
for E/B:

27640 cm-1/590 cm-1 = 46.8; ratio of two transitions is

impossible to determine since off scale assume to be
incorrect

27640 cm-1/780 cm-1 = 35; transition ratio 44/35 = 1.25

23400 cm-1/590 cm-1 = 39.7; transitio ratio 50/39.7 = 1.25
23400 cm-1/780 cm-1 = 30; transition ratio = 41/30 = 1.37

Hence, the other (lowest energy) transition must be

23400 cm-1 and B must = 780 cm-1.

b) Only two transitions are allowed because the third spin

allowed transition must be too high in energy.