Electronic Spectra of Complexes

[Co(H2O)6]2+
Oh, Pink

Many TM complexes show color, e.g.

[CoCl4]2Td, Blue

[Ni(H2O)6]2+ NH
3
Oh, Green

[Ni(NH3)6]2+
Oh, Blue

[Cr(H2O)6]3+
Oh, Violet

[Cr(H2O)6]2+
Oh, Bright Blue

Color is due to electronic transition b/w levels whose SPACING corresponds to

the wavelength of light available in visible region (complimentary color is
observed).

SPACING depends on:

- geometry of complex
- nature of ligands
- oxidation state of metal

Electronic Spectra: Examples

Electronic Spectra

MO diagram of octahedral
complex discussed so far
is based on one-electron
model

Configuration dn add effect of ee repulsion add effect of Ligand Field

Effect of e-e repulsion: Term Symbols

Splitting of Terms in Chemical Environment

(Transformation matrix)

(else 2l + 1)

(General Transformation matrix)

Construction of Correlation Diagram

Configuration dn add effect of ee repulsion add effect of Ligand Field

Correlation Diagram for a d2 system in Oh

(a) Free ion terms

(b) Weak field terms
(c) Strong field ground
and excited configuration
(d) Strong field terms
(e) Intermediate field

Total degeneracy
= (2l+1)*(2s+1)

Splitting of dn and d10-n Terms in Oh and Td Field

dn vs d10-n

Oh vs Td

Correlation Diagram for a d2 and d8 system

t
Octahedral d8 and
tetrahedral d2 on Left

O
Octahedral d2 and
tetrahedral d8 on Right

Correlation Diagram for a d4 system

Octahedral d10-n and tetrahedral dn on Left

Correlation Diagram for a dn system

(a) d2 and d8 (b) d3 and d7 (c) d4 and d6

(d) d5

Octahedral d10-n and tetrahedral dn on Left

Interpretation of Electronic Spectrum

Interpretation of Electronic Spectrum:
1. No. (and position) of spectral lines
2. Intensity of spectral lines
3. Width of spectral band

Selection Rules:
Laporte allowed transition are those with a change in parity
Spin allowed transition have same spin multiplicity

Molar absorptivities for various types of electronic transition

observed in complexes

Ground & excited terms having the same spin for weak field

Orgel Diagram
d3 system Co2+ ion
Td (right), Oh (left)

Tanabe Sugano Diagrams

Tanabe Sugano Diagrams

Info. From Tanabe Sugano Diagrams

d6 system

e.g. Low spin [Co(en)3]+

Info. From Tanabe Sugano Diagrams

Ratio = 1.32;
corresponds to D/B = 32.8
Gives B = 657/cm and D = 21550/cm

Info. from Tanabe Sugano Diagrams

d3