Content

• d-d transition,
• charge transfer transition,
• color, intensity and origin of spectra,
• interpretation,
• term symbols and splitting of terms different
geometries,
• selection rules for electronic transitions,
• correlation, Tanabe-Sugano and
Orgeldiagrams,
• calculation of Dq, B and C, nephelauxetic ratio.
Correlation diagrams

Correlation diagram for a d2 ion

in an octahedral environment
 =
15

1 1 3 1

1 1 3 1
1 3 1
3 1
 Correlation diagrams
Correlation diagram for a d2 ion Correlation diagram for a d ion 2

in an octahedral environment in an tetrahedral environment

 Tanabe Sugano Diagrams
Special correlation diagrams useful in the interpretation
of electronic spectra.
1. Vertical axis is the measure of the energy above the ground
state
E/B
2. Lowest energy state is plotted along the horizontal axis i.e.
the zero of energy .
o/B (field strength)
B = Racah parameter, B is the unit of energy

Advantage of using B as the unit of energy is that, same diagram may be used
for different values of B
 Parameters B and C are required to describe interelectronic repulsion
 Therefore C/B ratio must be specified for each diagram
 Diagrams have been compiled for most common first transition series
ions with most likely C/B
 This ratio affects only the relative energies of the excited states that
have different
spin multiplicities than the ground term
 We will be mostly concerned with the terms with same spin
multiplicities
 Same diagram may be used for any metal ion with the same
configuration
e.g. V2+ and Cr3+
 Equivalence of d10-n ≡ dn is valid
 Tanabe-Sugano diagrams.
d1 – d3 and d8 – d9 which have only high spin GS are easier. Here is d2.

Correlation diagram for d2. Tanabe-Sugano

Convert to Tanabe-Sugano.
From the information of The cystal-field theory (d2 configuration)

E(t22g, T1g) = 2(-2/5o) = -0.8 o

E(t12ge1g, T2g) = (-2/5+ -3/5) o = +0.2 o

E(e2g, A2g) = 2(3/5) o = +1.2 o

Therefore, relative to the energy of the lowest term, their energy are
E(t22g, T1g) =0 ; E(t12ge1g, T2g) = + o ; E(e2g, A2g) = +2 o

In summary, For a given metal ion, the energy of the individual terms
respond differently to ligands of incresing field strength and the
correlation between free atom terms of a complex can be displayed
on an Orgel diagram.
 Determining Do from spectra

d1
d9

Exciting d-hole Exciting

Exciting Exciting d-hole
from eg to t2g electron from t2g
electron from t2g from eg to t2g
to eg to eg
One transition allowed of energy Do
 Determining Do from spectra

Here the mixing is not a problem since

d3 mixing the “mixed” state is not involved in the
excitation.

mixing

d8

Lowest energy transition = Do

For d2 and d7 (=d5+d2) which involves mixing of the two T1g states, unavoidable problem.

Ground state and excited state

mixing which we saw earlier.

d2

But note that the

difference in
energies of two
excitations is Do.

d7

E (T1gA2g) - E (T1gT2g) = Do
Make sure you can identify the transitions!!
 Electronic transitions and spectra

d2 Tanabe-Sugano diagram

V(H2O)63+, a d2 complex
Can use T-S to calculate Ligand Field Splitting. Ex: d2, V(H2O)63+
Observed spectrum
u1: 17,800 cm-1
u2: 25,700 cm-1

Technique: Fit the observed energies to the diagram.

We must find a value of the splitting parameter, Do/B,
which provides two excitations with the ratio of
E/B 25,700/17,800 = 1.44

First, clearly u1 should correspond to 3T1  3T2 But note

that the u2 could correspond to either 3T1  3A2 or 3T1 
3
T1.
The ratio of u2/u1 = 1.44 is obtained at Do / B= 31

DO/B
Again, the root, basic problem Now can use excitation energies
is that the two T1 s have For u1: E/B = 17,800 cm-1 /B = 29 yielding B = 610
affected each other via mixing. cm-1
The energy gap depends to
By using 31 = Do/B = Do/610 obtain Do = 19,000 cm-1
some extent on the mixing!
The d5 case

All possible transitions forbidden

Very weak signals, faint color
 For all d configurations
First spin allowed transition
Spin forbidden bands

occurs exactly at or close to D

Except high spin d5
23840 cm-1

12660 cm-1

7400 cm-1

From the intensities of the bands

We come to know about the allowed 7400cm-1 3A2g 3
T2g =
and forbidden bands
12660 cm-1
A2g
3
T1g (F)
3

23840 cm-1
A2g
3
T1g (P)
3
Tanabe-Sugano diagrams

21
22
simplified Tanabe-Sugano diagrams
d2 d3 d4

d5 d6 d7

d8

23
Vibrational Spectroscopy

Group theory
Γ3N = 3A1 +A2 + 3B1 +2B2
25
 Normal Mode Analysis
Cartesian Coordinate Method
3N-6= 6 for N=4
28
 Normal Mode Analysis
Cartesian Coordinate Method
 Normal Mode Analysis
Cartesian Coordinate Method
 Normal Mode Analysis
Cartesian Coordinate Method
 Normal Mode Analysis

Cartesian

One A1’ mode in bending modes (angular coordinates) is extra and spurious
Normal Mode Analysis
Normal Mode Analysis
Normal Mode Analysis
36