Interpretation of UV-Vis

spectra of coordination
compounds
Warna senyawa kompleks
Electronic Configuration for Multielectrons Atoms

What is 2p2 ?

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

inter-electronic repulsions  energy differences

microstates

Term symbols of free atoms or ions, (2S+1)LJ

 Konfigurasi elektronik atom multi-elektron  pasangan RS
Russell-Saunders (or LS) coupling

Untuk tiap atom multi-elektron

Untuk tiap elektron 2p L = total orbital angular momentum quantum number
n = 2; 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 menyatakan microstates

• L/S menyatakan states (kumpulan
microstates)
• Group microstates dengan energi yang
sama disebut terms
Menentukan microstates untuk p2
Spin multiplicity = 2S + 1
 Menentukan harga L, ML, S, Ms untuk terms yang berbeda

1S

2P
 Mengklasifikasikan microstates 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 for ML = +1,
2S +1 = 3 (S=1)
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 (S=0)
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 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 (Hund’s 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
 before we did:

p2

ML & MS the largest ML L

spin multiplicity = Σcolumns
or 2S+1, S the largest MS
Microstate
Table
States (S, P, D)
Spin multiplicity

Terms
3P, 1D, 1S

Ground state term

3P
single e- (electronic state)  multi-e- (atomic state)
 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
Remember what we’re after ?

Theory to explain electronic

excitations/transitions observed for metal
complexes
 Franck-Condon approximation :
electronic transitions are very much faster than
nuclear motion (because nuclear mass is far greater than
electron mass)

Absorption bands in the electronic spectra of d-block metal

compounds are usually broad

The absorption of a photon of light occurs at 10–18 s whereas

molecular vibrations and rotations occur much more slowly.

As molecules are vibrating, an electronic transition is

essentially a snapshot at a particular set of internuclear
distances  the electronic spectrum will record a range of
energies  broad bands
 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

 Consequence of selection rule

Type of Typical max Example

transition (dm3mol-1cm-1)
d-d, spin <1 [Mn(OH2)6]2+
forbidden (high-spin d5)
d-d, spin allowed, 1-10 [Ti(OH2)6]3+ (d1)
Laporte forbidden 10-1000
Charge transfer 1000-50 000 [NiCl4]2-
 Ti3+

Beer-Lambert Absorption Law

log(Io/I)=A=lc (define variables)
In a common absorption spectrum, the A
is plotted versus wavelength or cm-1 (1/).
The absorption is characterized by max and max

• d1, d4, d6, d9 complexes  one broad absorption

• d2, d3, d7, d8 complexes  three broad absorption
• d5  a series of very weak, sharp absorption
Group theory analysis of term splitting
 Tanabe-Sugano Diagrams

• Special correlation diagrams useful in the

interpretation of electronic spectra.
– Lowest energy state is plotted along the horizontal axis.
• o/B (field strength)
– Vertical axis is the measure of the energy above the
ground state
• E/B
B = Racah parameter, a measure of the repulsion between terms
of the same multiplicity.
– Lines connecting states of the same symmetry cannot
cross.
Tanabe-Sugano diagrams

• show correlation of
spectroscopic transitions
observed for ideal Oh
complexes with electronic
states
• energy axes are
parameterized in terms of Δo
and the Racah parameter (B)
which measures repulsion d2
between terms of the same
multiplicity
d2 complex: Electronic transitions and spectra

only 2 of 3 predicted transitions

observed:
17800 cm-1
25700 cm-1

How to determine the o?

How to determine the third peak?
 d2 complex

1. Take the ratio of known

absorptions  25700/17800 =
1.44
2. Get the straight line of 2
possible transitions which the
length ratio is matching the
value of the above absorption
ratio (ratio absorption to the
lowest one)
1. Could be V3/V1 or
V2/V1
2. Assign the matching
one, eg: 1.44=V2/V1
3. Plotting the V2/V1 vs o/B
4. From the plot, At v2/v1 = 1.44
find the value of o/B
5. Extrapolated the value to get
E/B
At v2/v1 = 1.44, it is found the value
of o/B=31
From Tanabe-Sugano diagram:
 TS diagrams Other dn configurations

d3
d1 d9

d2 d8
 Other configurations

d3
The limit between
high spin and low spin
the spectra of dn hexaaqua complexes of 1st row TMs
 The d5 case

All possible transitions forbidden

Very weak signals, faint color
symmetry labels
 The electronic spectrum of [Ni(H2O)6]2+:
The complex looks green, because it absorbs only weakly at 500 nm,
the wavelength of green light.

UV visible infrared

[Ni(H2O)6]2+
3A
2g →1Eg
3A
2g →3T2g
green

λ,
 Electronic transitions:

eg eg
3A
3A
2g →3T2g 3T
2g 2g

t2g t2g

eg eg
3A
2g →1Eg
3A 1E
2g g

t2g t2g
ground state excited state
 Determining o from spectra

d1 d9

One transition allowed of energy o

 Determining o from spectra
mixing

mixing

Lowest energy transition = o

Ground state mixing

E (T1gA2g) - E (T1gT2g) = o
Energies of d-d Transitions

Octahedral d1, d4, d6 and d9:

1 band energy = oct

Octahedral d2:
3 bands oct and B from calculation

Octahedral d7:
3 bands oct = v2 – v1 B from calculation

Octahedral d3 and d8:

3 bands v1 = oct B from calculation
 Charge Transfer Transitions

• As well as ‘d-d’ transitions, the electronic spectra of transition metal

complexes may 3 others types of electronic transition:

 Ligand to metal charge transfer (LMCT)

 Metal to ligand charge transfer (MLCT)
 Intervalence transitions (IVT)

• All complexes show LMCT transitions, some show MLCT, a few show IVT
 Charge transfer spectra
Metal character

LMCT

Ligand character

Ligand character

MLCT
Metal character

Much more intense bands

 Ligand to Metal Charge Transfer
• These involve excitation of an electron from a ligand-based orbital
into a d-orbital

O O
visible light
M O M O
O O
O O

• This is always possible but LMCT transitions are usually in the ultraviolet
• They occur in the visible or near-ultraviolet if

 metal is easily reduced (for example metal in high oxidation state)

 ligand is easily oxidized

If they occur in the visible or near-ultraviolet, they are much more

intense than ‘d-d’ bands and the latter will not be seen
 Ligand to Metal Charge Transfer
•They occur in the visible or near-ultraviolet if

 metal is easily reduced (for example metal in high oxidation state)

TiO2 VO43- CrO42- MnO4-

Ti4+ V5+ Cr6+ Mn7+

d0 in far UV ~39500 cm-1 ~22200 cm-1 ~19000 cm-1

white white yellow purple

more easily reduced

 Metal to Ligand Charge Transfer
• They occur in the visible or near-ultraviolet if

 metal is easily oxidized and ligand has low lying empty orbitals

N
N N N
M
N N N
N N N

M = Fe2+, Ru2+, Os2+

• Sunlight excites electron from M2+ (t2g)6 into empty ligand p* orbital

 method of capturing and storing solar energy

 Intervalence Transitions
• Complexes containing metals in two oxidation states can be coloured
due to excitation of an electron from one metal to another

“Prussian blue”
contains Fe2+ and Fe3+

• Colour arises from excitation of an electron from Fe2+ to Fe3+

 Selection Rules and Band Intensity
• The height of the band in the spectrum is called the ‘molar
extinction cofficient’ – symbol :

 (mol-1 cm-1) type of transition type of complex

spin forbidden
octahedral d5 complexes
very 10-3 -1 orbitally forbidden,
pale colours (e.g. [Mn(H2O)6]2+)
Laporte forbidden
spin forbidden tetrahedral d5 complexes
1 – 10
orbitally forbidden, (e.g. [MnCl4]2-+)
spin allowed,
octahedral and square
10 – 102 orbitally forbidden
planar complexes
Laporte forbidden
spin allowed,
10 – 103 tetrahedral complexes
orbitally forbidden
intense
> 103 LMCT, MLCT, IVT
colours
24Cr: [Ar] 4s1 3d5 [Cr(NH3)6]3+
 Spectrochemical Series

• Strong–field ligands to weak–field ligands.

(large split) (small split)

CN– > NO2– > en > NH3 > H2O > OH– > F– > Cl– > Br– > I–

• Magnitude of split for a given ligand increases as

the charge on the metal ion increases.
Crystal-Field Theory

As Cr3+ goes from complexes with weak field ligands

to strong field ligands,  increases and the color of
the complex changes from green to yellow.
 d3
d
[V(H2O)6]2+ [V(H2O)6]3+

[Cr(NH3)6]3+ [Cr(NH3)5Cl]2+s
 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

 d1, d6 tetrahedral 0 d1, d6 octahedral 

d4, d9 octahedral d4, d9 tetrahedral

ligand field strength

 Free ion
term for
d2

Correlation
diagram: Relating
Electron Spectra to
Ligand Field
Splitting

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

Real complexes