Electonic Spectroscopy

Term Symbol and Corelation Diagram

1
Electronic (UV-visible)
Spectroscopy

｜ Electronic ｜
XPS UPS UV-visible

2
UV-visible spectroscopy
ligand *
(1) metal-metal (d-d) transition
*
metal-ligand metal d
(2) charge transfer (MLCT)
ligand-metal n
(LMCT) metal d
n
(3) ligand-centered transition ligand 

instrument sample

energy energy energy output
source selector analyzer

computer
electric connection
light path

absorbance Io
A = log ―― = cl
I
: extinction coefficient
c: concentration mol/L (M) 3
l: path length (cm)
selection rules
1. only one electron is involved in any transition
2. there must be no net change of spin S = 0

3. it must involve an overall change in orbital

angular momentum of one unit L = ±1
4. Laporte (or parity) selection rule
only g →u and u →g transitions are allowed
vibronic coupling – interaction between electronic
and vibrational modes

electronic transition 
Laporte allowed (charge transfer) 10000
(1000—50000)
Laporte forbidden (d-d transition)
spin allowed; noncentrosymmetiric 100—200
(200—250)
spin allowed; centrosymmetric 5—100
(20—100)
spin forbidden 0.01—1
4
(< 1)
 [CoCl4]2-

[Co(H2O)6]2+

[Mn(H2O)6]2+

5
d-d transition crystal field splitting

o size and charge of the metal ion and ligands

4d metal ~50% larger than 3d metal
5d metal ~25% larger than 4d metal
5d > 4d > 3d
crystal field stabilization energy (CFSE)
spin-pairing energy
high-spin/low spin configuration d4 ~ d7
d4

6
 other shapes
tetrahedral

t = 4/9 o

tetrahedron octahedron elongated square

octahedron planar

7
 d1 [Ti(H 2O)6]3+

ho

hole formalism

d2 possible electron
possible arrangements of electrons transitions

8
Russell-Saunders term symbols
for free atoms and ions 2S+1
LJ
S: total spin quantum number ms
L: total orbital angular quantum number ml
L = 0, 1, 2, 3, 4, …………..
S P D F G
1 3 5 7 9
J: total angular quantum number L+S, ……,│L-S│
d2 configuration 10!
———— = 45 microstates
8! 2!
S +1 0 -1
L
4 (2+ 2-)

3 (2+ 1+) (2+ 1-) (2- 1+) (2- 1-)

(1+ 1-)
2 (2+ 0+) (2+ 0-) (2- 0+) (2- 0-)
(1+ 0+) (1+ 0-) (1- 0+) (1- 0-)
1 (2+ -1+) (2+ -1-) (2- -1+) (2- -1-)
(0+ 0-)
0 (1+ -1+) (1+ -1-) (1- -1+) (1- -1-)
(2+ -2+) (2+ -2-) (2- -2+) (2- -2-)
1
G 3
F 1
D 3
P 1
S
9 + 21 + 5 + 9 + 1 = 45 9
ground term
states for dn systems in Russell-Saunders coupling

splitting of terms in various chemical

environments
d orbitals in Oh environment

consider pure rotational O subgroup

rotation by angle  ==> R(r), (), ψs invariant
only () will be altered
() = eim ==> () = eim(+ )
m = 2, 1, 0, -1, -2
e2ie2i+ )
eiei+ )
e0 ======>e0
e-ie-i+ ) 10
e-2ie-2i+ )
transformation matrix
e2i0 0 0 0
0 ei0 0 0
0 0 e0  0 0
0 0 0 e-i0
0 0 0 0 e-2i
sum of the diagonal elements
sin(l + 1/2)
() = ———————
sin(/2)

for d orbitals
sin(5/2)
() = 5 (C2) = ————— = 1
sin(/2)
sin(5/3) sin(5/4)
(C3) = ————— = -1 (C4) = ————— = -1
sin(/3) sin(/4)

==>  = eg + t2g

11
splitting of one-electron levels in an Oh environment

splitting of one-electron levels in various symmetries

12
determine the spin multiplicity of each term
d2 configuration in Oh environment
(i) t2g2 a
A1g + bEg + cT1g + dT2g
total degeneracy 15
a b c d
I 1 1 1 3
II 1 1 3 1
III 3 3 1 1

(ii) t2g1eg1 a
T1g + bT2g
total degeneracy 24
only possibility 1T1g 1T2g 3T1g 3T2g

(iii) eg2 a
A1g + bA2g + cEg
total degeneracy 6
a b c
I 1 3 1
II 3 1 1

1
S 1
A1g
1
G 1
A1g 1Eg 1T1g 1T2g
3
P 3
T1g
1
D 1
Eg 1T2g 13
3
F 3
A1g 3T1g 3T2g
method of descending symmetry
consider d2 ion in Oh environment
from correlation table for group O h

(i) t2g2 A1g Eg T1g T2g

lowering the symmetry to C2h t2g a g + ag + bg
t2g × t2g = 1
A1g 1
Eg 3
T1g 1T2g
possible spin 1 1 1 3
multiplicity 1 1 3 1 ˇ
3 3 1 1
corresponding 1
Ag 1
Ag 3
Ag 1
Ag
representations 1
Bg 3
Bg 1
Ag
in C2h 3
Bg 1
Bg
ag × ag Ag ====> 1
Ag
a g × a g’ Ag ====> 1
Ag 3 Ag
ag × bg Bg ====> 1
Bg 3 Bg
a g’ × a g’ Ag ====> 1
Ag
a g’ × b g Bg ====> 1
Bg 3 Bg
14
bg × bg Ag ====> 1
Ag
===> total 41A + 3A + 21B + 23B
(ii) eg2 A1g A2g Eg
lowering the symmetry to D4h eg a1g + b1g
a1g2 A1g possible spin multiplicity 1A1g
a1gb1g B1g possible spin multiplicity 1B1g 3B1g
b1g2 A1g possible spin multiplicity 1A1g
==> D4h Oh
1
A1g 1
A1g
3
B2g 3
A1g
1
A1g 1B1g 1
Eg

(iii) t2g1eg1 ????

consider d2 ion in Td environment

from splitting of energy level in Td symmetry
3
F 3
A2 3T1 3T2
1
D 1
E 1T2
3
P 3
T1
1
G 1
A1 1E 1T1 1T2
1
S 1
A1
electron configurations
e2 A 1 A2 E total degeneracy 6
et2 T 1 T2 total degeneracy 24
t22 A1 E T1 T2 total degeneracy 15
15

assign the correct spin multiplicity ???

splitting of the terms for d2 ion in several point
groups

16
correlation diagram for a d2 ion in Oh
environment

17
correlation diagram for a d2 ion in Td
environment

18
Orgel diagrams
d1, d6/d4, d9

 = 10 Dq d1, d6 octahedral
d1, d6 tetrahedral
d4, d9 octahedral d4, d9 tetrahedral
E T2 T2g Eg
Eg T2 g T2 E

19
 d2, d7/d3, d8

cm-1
d2, d7 tetrahedral Dq d2, d7 octahedral
d3, d8 octahedral d3, d8 tetrahedral
A2→T2 1 = 10Dq T1→T2 1 = 8Dq + c
A2→T1(F) 2 = 18Dq - c T1(F)→T1(P) 2 = 18Dq + c
A2→T1(P) 1 = 15B + 12Dq + c T1→A2 3 = 15B + 6Dq + 2c

20
21
Tanabe-Sugano diagrams

22
23
simplified Tanabe-Sugano diagrams

d2 d3 d4

d5 d6 d7

d8

24
magnitude of o
Mn(II) < Ni(II) <Co(II) < Fe(II) < V(II) < Fe(III)
< Cr(III) < V(III) < Co(III) < Mn(IV) < Mo(III)
< Rh(III) < Pd(IV) < Ir(III) < Re(IV) < Pt(IV)
o values for octahedral [M(H2O)6]n+ complexes
o (cm-1)
Ti3+ 20400 Mn3+ 21000 Co3+ 19000
V3+ 19000 Mn2+ 7500 Co2+ 9750
Cr3+ 17700 Fe3+ 21000 Ni2+ 8500
Cr2+ 12500 Fe2+ 10500 Cu2+ 12600
spectrochemical series
I- < Br- < -SCN- < Cl- < F- < urea < OH- < CH3COO-
< C2O4- < H2O < -NCS- < glycine < pyridine ~ NH3
< en < SO32- < o-phenanthroline < NO2- < CN- < PR3
< CO

ex. [Co(H2O)6]3+ o = 19000 cm-1

[Co(NH3)6]3+ o = 22900 cm-1
[Co(H2O)3(NH3)3]3+ o = ?
3/6 × 19000 + 3/6 × 22900 = 20950 cm-1

25
Jørgensen prediction of 10Dq and B
10Dq = f · g (cm-1 × 10-3)
B = Bo (1 － h · k)
Bo : free ion interelectronic repulsion parameter

Jahn-Teller distortions
distortion will occur whenever the resulting splitting
energy levels yields additional stabilization
__ dx -y
2 2 __ dz
2

eg __ __
__ dz 2 __ dx -y
2 2

or
__ dxy
__ __dxz, dyz
t2g __ __ __
__ __ dxz, dyz
26
__ dxy
 [M(H2O)6]n+

Ti3+ (d1) Mn2+ (d5)

V3+ (d2)

Fe2+ (d6)

Co2+ (d7)
Cr (d )
3+ 3

Ni2+ (d8)

Cu2+ (d9)

Cr2+ (d4)

27
d1

d2

28
d3

29
d3

30
d4

d5

31
d6

32
d6

33
d6

34
d7

35
d8

d9

36