1

LECTURE-11
,
STUDY MATERIAL CHEM-524
1. Orgel Diagrams, 2 Tanbe Sugano Diagrams
3. Interpretation of Crystal field Spectra
ReadingMaterial see, A. B. P.Lever Chapter 5, P-100-to-117
B. N. Figgis Chapter-7, p 160-to- 170 (very good, read it).
Youtube (Seach box-Christy Munir)
Google search the topics under-reference.

Orgel Diagrams
Orgel diagrams are also energy level diagram. They
are useful for showing the energy levels of both high
spin octahedral and tetrahedral transition metal ions.
Orgel diagrams show ONLY the spin-allowed
transitions of symmetry states of the highest spin
multiplicity.
For complexes with D ground term only one electronic
transition is expected. Following high spin
configurations give rise to D configuration and so are
easily dealt with help of orgel diagram:
d1, d4, d6 and d9.
 2

State Orgel Diagram

Orgel Diagram for free ion with ground state term ‘D’

↑
D
2

d
1
(1 unpaired electrons)

↑↓ ↑↓ d9 (1 hole & one hole) D

2
↑↓ ↑↓ ↑

↑ ↑ ↑ ↑ d4 (4 unpaired electrons) D
5

d (4 unpaired electrons & 4 holes)

↑↓
6
D
5
↑ ↑ ↑ ↑

D-State Orgel diagram:

On the left hand side
d1, d6 tetrahedral and
 3

d4, d9 octahedral complexes

are covered and on the right hand side d4,
d9 tetrahedral and d1, d6 octahedral.
For simplicity, the g subscripts required for the
octahedral complexes are not shown.

It is easy to understand and remember Orgel diagram.

Note, dn oct. ≡ d5+n oct

d1 oct. ≡ d6 oct.

Both d1 oct. and d6 oct. are shown on right side where

‘T’ is ground state and ‘E’ is excited state.

Also note, Note, dn oct. ≡ d10-n tet

d1 oct. ≡ d9 tet.

d1 Case: (ground state, G.S; Excited state, E.S)

__ __ (eg)0 ,A __ __ (eg)1 , E

__ __ __ (t2g)1 , T __ __ __ (t2g)0 , A
 4

G. S = T ⊗ A = T E. S = A ⊗ E = E
__________________________________________

d6 (H. S) Case:
__ __ (eg)2 , A __ __ (eg)3 , E

__ __ __ (t2g)4 , T __ __ __ (t2g)3 , A
G. S. = T⊗ A = T E. S. = A⊗ E = E
__________________________________________

d9 Case

__ __ (eg)3 , E __ __ (eg)4 , A

__ __ __ (t2g)6 A __ __ __(t2g)5 , T
G.S = A ⊗ E = E E. S. = T⊗ A= T
__________________________________________

Notice: In case of d1 oct., & d6 oct., both have same

G.S, i-e T; and same E.S, i-e E.
But in d9 case, the G.S is E (and not T) and E.S is T.
It is inverted. That is why we conclude that,
d1 oct. ≡ d9 tet. or
dn oct. ≡ d10-n tet
 5

For complexes with F ground terms, three electronic

transitions are expected and D may not correspond
directly to transition energy. The following
configurations are dealt with: d2, d3, high spin d7
and d8.

F State Orgel diagram

On left side: d2, d7 tetrahedral and d3, d8 octahedral.

On right side: d3, d8 tetrahedral and d2 and high spin

d7 octahedral

Again for simplicity, the g subscripts required for the

octahedral complexes are not shown.

TANABE-SUGANO DIAGRAMS
(T-S Diagrams)
 6

For a very long time little was known about the excited
electronic states of the free ions and their behavior
when it complexes with some ligands (Metal
Complexes). Only Hans Bethe's crystal field theory
was used for predicting UV-Visible spectra of complex
ions.
In 1954 Yukito Tanabe and Satoru Sugano published
their paper "On the absorption spectra of complex
ions", and explained the absorption spectra of
octahedral complex ions in a more quantitative way
than had been achieved previously.
These gentlemen calculated energies of varios terms
as a function of octahedral ligand field parameter,
10Dq or Δo and inter-electronic repulsion parameter ‘B,
the Racah parameter’. These diagrams allow calculations of
all energy levels of dn system in the presence of
Ligand field parameter 10Dq (or Δo) and inter-
electronic repulsion parameters ‘B’ & ‘C’.
7
 8

T. S diagram shown above contains both singlet and triplet

states. E/B is plotted against Triplet states (3T2g, 3T1g
and 3A2g) are shown with red line,
Below is given plots E/B vs Δo/B. with triplet stats only.
We also have plots E/B vs Dq/B.
 9

Two essential features of Tanabe-Sugano Diagram.

1. It is a plot of 10Dq/B (or Δo/B) and E/B. Thus the fact
that B is a function of Ligand field and metal is built in.
Thus T. S. diagram can be used for any combination
of metal and ligands.

2. In T-S diagrams ground state is always made the

horizontal line. Thus transition energies can be
estimated by simply vertical measurements from the
base line.

T-S diagrams are used to predict absorptions bands in

the UV, visible spectra of coordination compounds.
The results from a Tanabe–Sugano diagram analysis
of a metal complex can also be compared to
experimental spectroscopic data. They are
qualitatively useful and can be used to determine,
a.Ligand Field Splitting parameters, 10 Dq or Δo.
b.Inter-electronic repulsion parameter,
Racah Parameter B & C.
c. Ionic/covalent character of bonds. Beta β
d.Tanabe–Sugano diagrams can also be used to
predict the strength of the ligand field (10 Dq)
necessary to cause high-spin to low-spin
transitions.
 10

e.In a Tanabe–Sugano diagram, the ground state

is used as a constant reference. The energy of
the ground state is taken to be zero for all field
strengths, and the energies of all other terms
and their components are plotted with respect to
the ground term.

To be continued in Lecture-12.