Coordination Chemistry

Electronic Spectra of Metal Complexes

Electronic spectra (UV-vis spectroscopy)
Electronic spectra (UV-vis spectroscopy)

hn
DE
The colors of metal complexes
Electronic configurations of multi-electron atoms

What is a 2p2 configuration?

n = 2; l = 1; ml = -1, 0, +1; ms = 1/2

Many configurations fit that description

These configurations are called microstates

and they have different energies
because of inter-electronic repulsions
 Electronic configurations of multi-electron atoms
Russell-Saunders (or LS) coupling

For the multi-electron atom

For each 2p electron L = total orbital angular momentum quantum number
n = 1; l = 1 S = total spin angular momentum quantum number
ml = -1, 0, +1 Spin multiplicity = 2S+1
ms = 1/2
ML = ml (-L,0,+L)
MS = ms (S, S-1, ,0,-S)

ML/MS define microstates and L/S define

states (collections of microstates)
Groups of microstates with the same
energy are called terms
Determining the microstates for p2
Spin multiplicity 2S + 1
 Determining the values of L, ML, S, Ms for different terms

1S

2P
 Classifying the microstates for p2

Largest ML is +2,
so L = 2 (a D term)
and MS = 0 for ML = +2,
2S +1 = 1 (S = 0)
1D

Next largest ML is +1,

so L = 1 (a P term)
and MS = 0, 1/2 for ML = +1,
2S +1 = 3
3P

One remaining microstate

ML is 0, L = 0 (an S term)
and MS = 0 for ML = 0,
Spin multiplicity = # columns of microstates 2S +1 = 1
1S
 Next largest ML is +1,
Largest ML is +2,
so L = 1 (a P term)
so L = 2 (a D term)
and MS = 0, 1/2 for ML = +1,
and MS = 0 for ML = +2,
2S +1 = 3
2S +1 = 1 (S = 0) 3P
1D

ML is 0, L = 0
2S +1 = 1
1S
 Energy of terms (Hunds rules)

Lowest energy (ground term)

Highest spin multiplicity
3P term for p2 case

3P has S = 1, L = 1

If two states have

the same maximum spin multiplicity
Ground term is that of highest L
Determining the microstates for s1p1
Determining the terms for s1p1

Ground-state term
 Coordination Chemistry
Electronic Spectra of Metal Complexes
cont.
 Electronic configurations of multi-electron atoms
Russell-Saunders (or LS) coupling

For the multi-electron atom

For each 2p electron L = total orbital angular momentum quantum number
n = 1; l = 1 S = total spin angular momentum quantum number
ml = -1, 0, +1 Spin multiplicity = 2S+1
ms = 1/2
ML = ml (-L,0,+L)
MS = ms (S, S-1, ,0,-S)

ML/MS define microstates and L/S define

states (collections of microstates)
Groups of microstates with the same
energy are called terms
 before we did:

p2

ML & MS

Microstate
Table
States (S, P, D)
Spin multiplicity

Terms
3P, 1D, 1S

Ground state term

3P
 For metal complexes we need to consider
d1-d10

d2

3F, 3P, 1G, 1D, 1S

For 3 or more electrons, this is a long tedious process

But luckily this has been tabulated before

Transitions between electronic terms will give rise to spectra
 Selection rules
(determine intensities)

Laporte rule
g g forbidden (that is, d-d forbidden)
but g u allowed (that is, d-p allowed)

Spin rule
Transitions between states of different multiplicities forbidden
Transitions between states of same multiplicities allowed

These rules are relaxed by molecular vibrations, and spin-orbit coupling

Group theory analysis of term splitting
 An e electron
superimposed
High Spin Ground States on a spherical
distribution
energies
dn Free ion GS Oct. complex Tet complex
reversed
d0 1S t2g0eg0 e0t20 because
d1 2D t2g1eg0 e1t20 tetrahedral
d2 3F t2g2eg0 e2t20
d3 4F t2g3eg0 e2t21
d4 5D t2g3eg1 e2t22

Holes in d5 d5 6S t2g3eg2 e2t23

and d10, d6 5D t2g4eg2 e3t23

reversing d7 4F t2g5eg2 e4t23
energies d8 3F t2g6eg2 e4t24
relative to
d9 2D t2g6eg3 e4t25
d1
d10 1S t2g6eg4 e4t26

Holes: = dn d10-n
and neglecting spin = dn d5+n;
same A t2 hole in d5,
splitting but reversed energies because positive. reversed energies,
reversed again
Expect oct d1 and d6 to behave same as tet d4 and d9
relative to
Expect oct d4 and d9 (holes), tet d1 and d6 to be reverse of oct d1 octahedral since tet.
 d1 d6 d4 d9

Orgel diagram for d1, d4, d6, d9

Eg or E
T2g or T2

Energy D

T2g or T2
Eg or E

D d1, d6 tetrahedral 0 d1, d6 octahedral D

d4, d9 octahedral d4, d9 tetrahedral

ligand field strength

Orgel diagram for d2, d3, d7, d8 ions

Energy

A2 or A2g

T1 or T1g
P T1 or T1g

T1 or T1g T2 or T2g
F

T2 or T2g

T1 or T1g

A2 or A2g

d2, d7 tetrahedral 0 d2, d7 octahedral

d3, d8 octahedral d3, d8 tetrahedral
Ligand field strength (Dq)
 d2

3F, 3P, 1G, 1D, 1S

Real complexes
Tanabe-Sugano diagrams

d2
Electronic transitions and spectra
 Other configurations

d3
d1 d9

d2 d8
 Other configurations

d3
The limit between
high spin and low spin
 Determining Do from spectra

d1 d9

One transition allowed of energy Do

 Determining Do from spectra
mixing

mixing

Lowest energy transition = Do

Ground state mixing

E (T1gA2g) - E (T1gT2g) = Do
The d5 case

All possible transitions forbidden

Very weak signals, faint color
Some examples of spectra
 Charge transfer spectra
Metal character

LMCT

Ligand character

Ligand character

MLCT
Metal character

Much more intense bands