5.

04, Principles of Inorganic Chemistry II

MIT Department of Chemistry
Lecture 30: Tanabe Sugano Diagrams

TS diagram plots energy dependence of term with field strength for a given
B/C ratio. Both term energy and field strength are normalized to B. The
lowest energy term is set = 0… so for hs/ls systems, there will be a
discontinuity

(hs)

(ls)
E
B

(ls)
(hs)

Dq/B

Let’s consider electronic spectra of aquo complexes of first row TMs

d1, Ti3+ (
max = 20300 cm-1,  ~ 4 M-1cm-1)

2
Eg
only one possible transition (the shoulder
in the spectrum is due to Ti(H2O)5(OH)2+)…
so this is a trivial solution
2
D 10 Dq
E
=10 Dq=20300 cm-1 , Dq=2030 cm-1
B
2
T2g

5.04, Principles of Inorganic Chemistry II Lecture 30

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d9, Cu2+ (
max = 12000 cm-1,  ~ 11 M-1cm-1

2
T2g
again expect only one band, but clearly
there are two… this due to a Jahn-Teller
distortion
2
D 10 Dq

2
Eg

Jahn-Teller effect - a molecule with an orbitally degenerate ground state will

distort to remove the degeneracy and consequently lower its overall energy

2+ OH2 2+
OH2
H2O OH2 H2O OH2
Cu Cu
H2O OH2 H2O OH2
OH2
OH2

eg b1g

a1g

teg eg
b2g

2
B2g

2
T2g
2
Eg
2
D
2
A1g
2
Eg

2
B1g

Generally, a JT effect most pronounced when M-L * orbitals are involved.

5.04, Principles of Inorganic Chemistry II Lecture 30

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d2, V3+ (max = 17200 cm-1,  ~ 6 M-1cm-1; max = 25600 cm-1,  ~ 8 M-1cm-1)
from d2 configuration, get terms of 3F, 1D, 3P, 1G and 1S … spin allowed
transition (
S = 0) will prevail (i.e., be the most intense). Thus we will
assume that transitions are between states from the terms, of 3F and 3P since
the 3F is the ground state

2 3
P T1g
3
A2g this corresponds to a 2e- transition…
therefore transitions to this state
10 Dq should be exceptionally weak (due to
low absorption cross-section… i.e.
3 isospatial and isotemporal is very
T2g
3
unlikeley
F 8 Dq
3
T1g

Most reasonable assignments therefore are:

E 3 T1g (P)
3 T1g (F )

( ) 25600
= = 1.49
E( 3
T2g (F )
T1g
3
(F )) 17200

From the TS diagram, this ratio is best fit at Dq/B = 2.8. At this energy value

E 3 T2g (F�
( ) ) 17, 200 cm
1
= 25.9 = or B = 664 cm-1�
B B

E 3 T1g (P)
( ) 25, 600 cm
1
= 38.7 = or B = 661 cm-1
B B

Bavg = 663 cm-1

5.04, Principles of Inorganic Chemistry II Lecture 30

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 Energy diagram for d2. C/B = 4.42.
Figure removed due to copyright considerations.

Dq
= 2.8  Dq = 2.8(B) = 2.8 663 cm
1 = 1860 cm
1
( )
B

Thus 10Dq = 18600 cm-1

From the fit Dq and B values, may now determine energies of all other
transitions (including the spin for bidden ones) of V(H2O)63+. The 2e
transition should fall at…

E 3 A 2g (F )
3 T1g (F )
( ) = 54 at Dq/B = 2.8
B

E(3A2g(F)
3T1g(F)) = 54 (662 cm-1) = 35800 cm-1

Note: the B value for V3+ complexed by H2O is smaller than the free ion value
of 860 cm-1. Remember B is a measure of the interelectronic repulsion… in
the complex, the metal d orbitals mix with the ligand orbitals. Owing to the
covalency, the spatial dimension of the orbitals in which the d-electrons

5.04, Principles of Inorganic Chemistry II Lecture 30

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 1�
reside increases… since operator for interelectronic repulsion goes as … as
rij
rij increases, interelectronic repulsion decreases and hence B decreases.

5.04, Principles of Inorganic Chemistry II Lecture 30 �

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