SPECTRAL CALCULATION

OF ORGEL AND TANABE-

SUGANO DIAGRAM’S

VISHAL P. TIWARI
ROLL NO : 06
MSC PART 1, CHEMISTRY
SS &LS PATKAR VARDE COLLEGE
WHAT IS A ORGEL DIAGRAM
An energy level diagram showing the splitting
of the terms of the terms as a function of weak
octahedral or tetrahedral field will help of for
a simple interpetation of crystal field spectra
which originates from d-d transition metal
complexs. Such as diagram is known as orgel
diagram.
only two diagrams are sufficient for the
interpretation of the spin allowed crystal field
transition under the influence of octahedral
and tertahedral fields.
 1. d1 metal ion in octahedral ligand environment

For example Ti(III),Octahedral complex such as [Ti(H2O)6]3+

for free metal ion the ground state term for d1 configuration is 2D
 In ligand field (OH) field has one electron in T2g orbital
Triply degenerate (dxy1 or dyz1 or dxz1 ) therefore ground state as assign
T2g
In excited state electron occupies Eg energy level (doubly degenerate)
i.e. dz2 or dx2-y2
 2T2g 2E
g transition
The absorption spectrum shows only one band peak at 20400 cm-1
The absorption band in the spectrum appears composite because of
the splitting of the excited state due to john-teller effect
 1. d9 metal ion in octahedral ligand environment

For example [Cu(H2O)6]2+ with Cu2+ ions (3d9)

For free metal ion, the ground state term is 2D. In the d9
configuration there is the single hole in upper Eg level
Movement of hole from 2Eg to 2T2g level transition. The ground
state originates from T2g6 Eg3 configuration which is doubly
degenerate
The excited state originates from t2g5 eg4 and is triply
degenerate
The composite nature of the band due to john-teller
distortion and It is 12000 cm-1
 1. d6 metal ion in octahedral ligand environment

For example [Fe(H2O)6]2+

d6 octahedral arrangement t2g4eg2 is related to d1 case

For free metal ion, the ground state term is 5D.

In OH field the electronic transition at ground state triply

degenerate t2g4eg2 to excited state doubly degenerate t2g3eg3 .
The absorption band is therefore assigned to 5T2g →5Eg
transition (spin multiplicity is 5)
The band appears to be composite one due to the splitting of
the excited state energy level into non degenerate levels due to
john teller distortion and it is 10000 cm-1
 1. d4 metal ion in octahedral ligand environment

For example [Cr(H2O)6]2+

It is an considered as similar d9 configuration with one hole in
the eg level.
The ground state5Eg originates from doubly degenerate t2g3eg1
and the excited state 5 T2g originate from triply degenerate
configuration t2g2eg2 .
Therefore absorption band is assigned to 5Eg →5 T2g transition.

Shows absorption band around 14000 cm-1

1. d2 metal ion in octahedral ligand environment

In this the ground state 3F and excited states 3P,1G,1D, 1S .

3F contains electrons with parallel spin and other opposite
spins here transition very weak that’s why ignored .
Two electrons occupied in the t2g orbital .E.C - t2g2eg0 .

Three transition are possible

3T
1g(F)→ T2g(f)
3

3T
1g(F)→ T1g(P)
3

3T
1g(F)→ A2g(F)
3
 1. d8 metal ion in octahedral ligand environment

Two holes are observed in eg level

E.C - t2g6eg2
Upper diagram is is inverse of d2
 1. d7 metal ion in octahedral ligand environment

Ground state triply degenerated

E.C. - t2g5eg2
D7 nearly similar to d2
1. d3 metal ion in octahedral ligand environment

In that ground state is single degenerated .

E.C. - t2g3eg0 .
It is same as d8 but inverse of d2 and d7 metal ion .
 TANABE-SUGANO DIAGRAMS
A free metal ion →weak octahedral field
→strong octahedral field environments are
known as TANABE – SUGANO DIAGRAMS
These diagrams are essentials for interpreting
electronic abosrption spectra of complexes.
Make using B&C parameter
Calculation of energies are dependent upon
C/B ratios .
In diagram Dq/B is represented by the
horizontal axis and vertical axis E/B.
Ground term always located on the horizontal
axis.
 EXAMPLE OF TANABE SUGANO DIAGRAM

In the diagram certain break point due to high spin multiplicity from
there system starts increasing energy.
In the diagram left side of break point complex occur high spin and
other right hand low spin
 CALCULATION OF ELECTRONIC PARAMETER
EXAMPLE
[V(H2O)6] has absorption band at 17800 and 25700 cm-1. Using the tanabe-
sugano diagram for d2, estimated values of ∆◦ and B for this complex
From the tanabe sugano diagram there are three possible spins-allowed
transitions
3T (F) →3T (F ) v1
1g 2g
3T (F) →3T (P) v2
1g 1g
3T (F) →3A (F) v3
1g 2g
When working with spectra ,it is often useful determine the ratio of energies
of the absorption bands in this example
25700 cm-1 /17800 cm-1 = 1.44
The ratio of energy transition (v2 or v3)to the lowest energy transition (v1)
must therefore be approximate 1.44. from the tanabe-sugano diagram we can
see that the ratio of v3 to v1 is approximate 2 , regardless of the strength of
the ligand field ; we can therfore eliminate v3 as the possible transition
occuring 25700 cm-1 this mean that the 25700 cm-1 band must be v2 ,
corresponding to 3T1g (F) →3T1g (P) ,and
1.44 = v2 / v1
The ratio v2 / v1 varies as a function of the ligand field. By plotting the ratio v2
/ v1 versus∆◦ /B . we find v2 / v1 =1.44 at approximate ∆◦ /B =31
At ∆◦ /B =31 :
v2 : E/B = 42 (approximate) B = E/42 = 25700 cm-1 /42 = 610 cm-1

v1 : E/B = 29 (approximate) B = E/29 = 17800 cm-1 /29 = 610 cm-1

because ∆◦ /B =31
∆◦ = 31×B = 31×610 cm-1 = 19000cm-1
 RACAH PARAMETERS
 Interelectronic repulsion can be expressed
in terms of three parameters A, B and C
which are known as the Racah parameters
after Giulio Racah, who first described them.
‘A’ = average total interelectronic repulsion.
It is constant among d-electron configuration
‘B ’and ’C’ correspond with individual d-
electron repulsions
They are generally obtained empirically
from gas-phase spectroscopic studies of atoms
 NEPHELAUXETIC RATIO
Racah parameters were generated as a
means to describe the effects of electron-
electron repulsion within the metal
complexes. ... Comparisons between
tabulated free ion B and B of a
coordination complex is called
the nephelauxetic ratio (the effect of
reducing electron-electron repulsion via
ligands)
The name "nephelauxetic" comes from
the Greek for cloud-expanding.
 REFERENCES
1)B.R. Puri ,L.R. Sharma & K.C. Kalia ,
principal of Inorganic chemistry,
Milestone Publishers ,2013-14
2)J.Huheey ,F.A.Keiter & R.L. Keiter ,
Inorganic chemistry: Principal of
structure and reactivity, Pearson
Education ltd ,2006
3) Tybsc text book of inorganic chemistry
,himalaya publication ,2016