NPTEL – Chemistry and Biochemistry – Coordination Chemistry (Chemistry of transition

elements)

Tanabe-Sugano Diagrams
K.Sridharan

Dean

School of Chemical & Biotechnology

SASTRA University

Thanjavur – 613 401

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Table of Contents
1 Orgel Diagram............................................................................................................................... 3
1.1 Ground and excited terms with the same multiplicities for weak field octahedral and
tetrahedral complexes ................................................................................................................ 5
2 Orgel diagrams ............................................................................................................................. 6
2.1 Characteristics of the diagram .............................................................................................. 6
2.2 How to use this diagram? ...................................................................................................... 7
2.2.1 Order of transitions based on energy ............................................................................ 7
3 Tanabe-Sugano diagrams ............................................................................................................. 8
3.1 Explanation about the different energy levels in the diagram.............................................. 8
4 References .................................................................................................................................. 10

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1 Orgel Diagram
Normally, our requirement will be to find out how many spin-allowed transitions
are possible for a given complex and what are they so that their electronic
spectra can be interpreted. In this regard, we must know what are the ground
and different excited states with their multiplicity for the complex.
Example 1 [V(H 2 O) 6 ]3+
The electronic spectrum of this complex is given in Figure 1.1.

17500 cm-1 25,000 cm-1

Absorbance

ν, cm-1
Fig 1.1 Absorption spectrum of [V(H 2 O) 6 ]3+

This spectrum shows two absorption maxima indicating that there are two
transitions for this complex and two excited states are there. These two are
identified as follows:
Step 1: Find out the oxidation state of the central metal atom in the complex
and hence the dn system
vanadium is in the +3 state in this complex
Electronic configuration of V is: 3d34s2
Electronic configuration of V3+ is: 3d2
This complex is an octahedral complex (because six aquo ligands are there)

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and a d2 system.
Step 2: Find out the ground term of the free ion and how it is split into
various energy levels in an octahedral field
The ground state for a d2 system is 3F. This is split in an octahedral field as
shown in Figure 1.2.
3A
2g

3T
2g

3F

3T
1g

Fig 1.2 Splitting of an F term in an octahedral field

Step 3: Find out how many excited states with the same multiplicity are there
and hence, how many transitions.
3 3
Two excited states with the same multiplicities are there: T 2g and A 2g .
Therefore, two spin-allowed transitions are possible:
3 3
T 1g T 2g will have lower energy and 3T 1g 3
A 2g will have higher energy.

Step 4: Based on these can we assign the spectral bands to the transitions?
No, because we have not considered the other terms coming from the
excited states and how these are affected by ligand fields. In the excited
3
states, leaving those with multiplicities other than 3, we have got one P
3
state in the free ion, which also transforms as F state in the octahedral
3
field. This is represented as F(P). Hence, one more transition is possible for
this complex, viz., 3T1g 3 F(P).

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Step 5: Correct assignment of transitions

This can be done only when we understand the effect of ligand fields on
these terms. For example, the 3 F(P) will be having higher energy than 3F in
weak field case, that is, the ligands will be weak ligands. However, when the
ligand field strength increases, the energy of 3F(P) decreases and at a particular
time, it has a lower energy than 3F. Under these circumstances, the second
transition will be 3 T1g 3F(P) and not 3 T1g 3F. Thus, the variation of
energy of terms with respect to ligand field must be known to assign the
transitions correctly.

1.1 Ground and excited terms with the same multiplicities for
weak field octahedral and tetrahedral complexes
Configuration Ground term Excited terms with the same spin multiplicity as the
(g subscripts ground
for octahedral term
complexes only

d1 oct, d9 tet 2
T2g 2
E2g
d2 oct, d8 tet 3
T1g(F) 3
T2g, 3A2g, 3T1g (P)
d3 oct, d7 tet 4
A2g 4
T2g, 4T1g(F), 4T1g(P)
d4 oct, d6 tet 5
E2g 2
T2g
d5 oct, d5 tet 6
A1g -
d6 oct, d4 tet 5
T2g 5
E2g
d7 oct, d3 tet 4
T1g(F) 4
T2g, 4A2g, 4T1g(P)
d8 oct, d2 tet 3
A2g 3
T2g, 3A1g(F), 3T1g(P)
d9 oct, d1 tet 2
E2g 2
T2g

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2 Orgel diagrams
This diagram helps in predicting the number of transitions expected in an
electronic spectrum (UV-vis) for a complex.

2.1 Characteristics of the diagram

This represents the ground and excited states of the same multiplicity for a
particular configuration. Excited states of other multiplicities are not considered
and hence the diagram is simple. This diagram considers only weak field
octahedral and tetrahedral cases. This illustrates the effect of mixing of terms,
that is, terms having identical symmetry will mix and upper level will increase in
energy and lower level will decrease in energy. Terms having different
symmetries will cross, while terms having identical symmetries will not cross.

A2
T1 T1
P

T2
T1

T2
F
T1

A2
Dq 0 Dq

Td Oh Td Oh

d2, d7 d3, d8 d3, d8 d2, d7

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2.2 How to use this diagram?

For example we want to predict the number of transitions for a d2 system. Go to
the right side of the diagram because Oh-d2 is there.
The ground term is T 1 arising from the F term of the free ion. Hence, it is
denoted as 3T 1g (F). Then the probable number of transitions will be:
3T 3T
1g(F) 2g
3T 3T (P)
1g(F) 1g
3T 3A
1g(F) 2g

2.2.1 Order of transitions based on energy

Among the three, the lowest energy transition will be obviously
3 3
T 1g (F) T 2g ,
Which is the next transition amongst the other two depends on the Dq
value (ligand field strength) as evident from the figure. Till certain point, 3 A 2g
has the lower energy than 3 T 1g (P). Hence, in this range of Dq,
3 3
T 1g (F) A 2g will be the second transition. After this point, 3T 1g (P) term falls
in energy and the order is reversed. Hence, 3T1g(F) 3
T1g(P) will be the
second transition.
Thus, the Orgel diagram of a particular system helps in predicting the
transitions and their order of energy in the electronic spectrum or when the
spectrum is available, it can be interpreted.

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3 Tanabe-Sugano diagrams
This diagram results when the energy of various terms are plotted against B,
where B is the Racah parameter (interelectronic repulsion parameter). This
diagram includes strong field cases also and hence more useful and
understandable than Orgel diagrams. Quantitative information can be obtained
from this diagram. The free ion terms are shown on the y-axis: 5D, 3H, 1I, 1F.
The terms arising from these in an octahedral field are shown by the appropriate
letters. Weak field complexes are to left of the vertical line in the middle and the
strong field cases are on the right of the vertical line in the middle.

3.1 Explanation about the different energy levels in the diagram

5
D gives rise to two terms, viz.,5T 2g and 5E g in the octahedral field. 5T 2g is the
ground state in the weak field case and after the middle vertical line its energy
increases and it is not a ground state in the strong field case. Instead, 1 A 1g
originating from a 1 I term having a higher energy in the weak field case is
having the minimum energy in the strong field case and is the ground state. In
this manner, we can easily understand the variation of energy of various levels
with ligand field strength from the diagram.
The number of transitions and hence the absorption in the UV-vis spectrum of a
complex can be easily predicted / assigned from this diagram.
The diagram is for a d6 system.is shown in Figure 3.1.1. From this diagram,
weak and strong field spectra can be assigned for Co(III) complexes. Thus, for
CoF 6 3-, there will be only one transition, viz., 5T 2g 5E
g and in the case
of Co(NH3) 6 3+, there will be a minimum of two transitions, viz.,1A 1g 1T
1g

and 1A 1g 1T
2g . These are shown by vertical arrows in the diagram. These
are the spin-allowed transitions.

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5E 1A
g 2g
1A
2g
1E
g
3E
1F g
1T
2g

5T
2g
1T
1I 1g

1A
1g 3T
2g
3T
1g

3H

5E
g

5T 1A
5D 2g 1g

∆/B

Fig 3.1.1 Tanabe-Sugano diagram for d6 octahedral complex

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4 References
1. “Inorganic Chemistry: Principles of Structure and Reactivity”, James
E.Huheey, Ellen A.Keiter, Richard L.Keiter, Okhil K.Medhi, Pearson
Education, Delhi, 2006
2. “Inorganic Chemistry”, Shriver and Atkins, 3/e, Oxford University Press,
2002,
3. “Concise Inorganic Chemistry”, 5/e, Blackwell Science, 2005,
4. “Concepts and Models of Inorganic Chemistry”, 3/e, John Wiley & Sons

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