K

I
N
O
S
R
K
T
E
K
L
E
P
L
E
i
M
s
i
O
s
A
n
K
R
a
r
T
T
A
K
m
W
E
a
g
A
P
o
L
S NY
a
w
SE
ya
n
e
S

Dr. rer. Nat. Agustino Zulys M.Sc.

1

03/14/16

Departemen Kimia Fakultas Matematika dan Ilmu Pengetahuan Alam Universitas

Indonesia

Langkah penentuan Ground Term

p2
ML & MS
Microstate
Table
States (S, P, D)
Spin multiplicity
Terms
3
P, 1D, 1S
Ground state term
3
P

Untuk senyawa kompleks logam transisi

Mempertimbangkan d1-d10

d2
3

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

Untuk 3 atau lebih elektron adalah proses yang sangat panjang

Zum Glck is schon tabuliert vorher

Transitions antara term electron memberikan spektra elektronik

Yang mana keadaan dasar?

3

P
Keadaan2 yang
memiliki spin
multiplicity yang
sama

E
3

E = 15 B
B adalah parameter Racah dan pengukuran tolakan antar elektron
dalam ion

Kekuatan relatif interaksi kopling:

MS = ms

>

ML = ml

>

ML - MS

Apakah keadan dasar term untuk konfigurasi p2 dan d2?

d7:

P 4F

P 2D 2F 2G 2H

Keadaan dasar 4P 4F karena memiliki spin multiplicity terbesar

d5:

P 4F

P 2D 2F 2G 2H

S 2D 2F 2G 2I

D 4G

Keadaan dasar ion bebas dn

d3

d4

d5

d6

-2

-2

-2

-2

-1

-1

-1

-1

ML = -33

L=3

F term

MS = 3/2

2S+1 =

ML = -22

L=2

D term

MS = 4/2

2S+1 =

ML = 0

L=0

S term

MS = 5/2

2S+1 =

ML = -2.2

L=2

D term

MS = 2

2S+1 =

Keadaan dasar ion bebas dn

d7

d8

d9

-2

-2

-2

-1

-1

-1

ML = -3.3

L=3

F term

MS = 3/2

2S+1 =

ML = -3.3

L=3

F term

MS = 2/2

2S+1 =

ML = -22

L=2

D term

MS = 1/2

2S+1 =

Keadaan dasar ion bebas dn untuk semua konfigurasi

Ground State
d1

d9

d2

d8

d3

d7

d4

d6

d5

d-d transitions in high spin complexes

Efek medan kristal pada term ion bebas untuk kompleks d1

d1 d6

tetrahedral field

free ion

octahedral field
Eg

T2

6 Dq
4 Dq
2
T2g

Diagram tingkat energi diagram

untuk ion d1 pada medan Oh field
Eg

Energy

T2g

ligand field strength, oct

Untuk ion d6 pada medan oktaheral menghasilkan spiliting yangsama dengan d1, tetapi
multiplicity nya 5, yaitu 5Eg and 5T2g

Diagram tingkat energi diagram

untuk ion d1 pada medan Oh field
T2g

Energy
6 Dq
2

4 Dq
Eg

ligand field strength, oct

Kompleks d9 memiliki tingkat energi yang sama dengan kompleks d1, tetapi
urutannya kebalikan
d4 d9

d1 d6

d4 d9

Diagram Orgel untuk d1, d4, d6, d9

Eg

Energy

or

T2g or T2
D

T2g

or

T2

Eg or E

d1, d6 tetrahedral
d4, d9 octahedral

d1, d6 octahedral
d4, d9 tetrahedral

ligand field strength

d1 oct

[Ti(OH2)6]3+

Eg

Eg 2T2g

T2g

10 000

20 000

30 000
- / cm-1

Diagram Orgel untuk d1, d4, d6, d9

Eg or E

E
T2g or T2
D

T2g or T2

Eg or E

d1, d6 tetrahedral
d4, d9 octahedral

d1, d6 octahedral
0
d4, d9 tetrahedral
LF strength

Effect medan ligand pada

keadaan
dasar
GS
free ion

d1

d9

d2

d8

d3

d7

d4

d6

d5

P
P

free ion

GS
d1

d9

d2

d8

d3

d7

d4

d6

d5

D
F

D
S

ligand field

T2(g) and E(g)

ligand field

?
F

Analisis Teori Group pada pemecahan term (energi orbital)

medan oktahedral.
Term
S
P

Komponen dalam oktahedral

A1g
T1g

T2g + Eg

A2g + T2g + T1g

A1g + Eg + T2g + T1g

Eg + T1g + T1g + T2g

A1g + A2g + Eg + T1g + T2g + T2g

Catatan: analisis simetri dari orbital atom ketika mengalami spliting pada medan
oktahedral.

Octahedral d2 complex

d2 d7

P: high repulsion

xz + z2
yz + z2
xy + x2-y2

In a LF, these orbitals are unaffected

3

T1g

F: low repulsion

In a LF, orbitals in the t2g set go down in energy, orbitals in the eg set go up in energy
A2g

eg eg

singly degenerate, high energy

T2g

eg t2g

triply degenerate, medium energy

T1g

t2g t2g

triply degenerate, low energy

x -y + z
2

x2-y2 + yz
x2-y2 + xz
xy + z2

xy + xz
xy + yz
xz + yz

Octahedral d3 complex

(same terms, different spin)

P: high repulsion

In a LF, these orbitals are unaffected 4T1g

F: low repulsion

The order of energy levels is the opposite to that for a d2 ion

4

T1g

T2g

A2g

d3 d8

Orgel diagram for d2, d3, d7, d8 ions

Quantum Mixing
A2 or A2g

Energy

T1 or T1g

T1 or T1g

P
T1 or T1g

T2 or T2g

T2 or T2g
T1 or T1g
A2 or A2g
d2, d7 tetrahedral
d3, d8 octahedral

d2, d7 octahedral
0

d3, d8 tetrahedral

Ligand field strength (Dq)

Energy level diagram for oct d2, d7, tet d3, d8

T1(g)

15 B > 15 B'

P
A2(g)
15 B

15 B'
10 Dq
T2(g)
2 Dq

6 Dq
T1(g)

Calculating B' and x

d7 octahedral complex

[Co(H2O)6]2+

T1g

x
A2g

3
2

2
15 B'
10 Dq

T2g

v / cm-1

25 000

20 000

15 000

2 Dq
6 Dq

1 = 8 000 cm-1
2 = 16 000 cm-1

x
T1g

3 = 19 400 cm-1

10 000

Orgel diagram for d2, d3, d7, d8 ions

A2 or A2g
Energy

T1 or T1g

T1 or T1g

P
T1 or T1g

T2 or T2g

T2 or T2g
T1 or T1g
A2 or A2g
d2, d7 tetrahedral
d3, d8 octahedral

d2, d7 octahedral
0

d3, d8 tetrahedral

Ligand field strength (Dq)

Energy level diagram for oct d2, d7, tet d3, d8

A2(g)
3

1:

x + 8 Dq

2:

2 x + 6 Dq + 15 B'

3:

x + 18 Dq

T1(g)
2
P

15 B
F

x 10 Dq

15 B'

T2(g)
1

2 Dq
6 Dq

T1(g)

1:

T2(g) T1(g)

2:

T1(g)(P) T1(g)

3:

A2(g) T1(g)

Energy diagram for oct d3, d8, tet d2, d7

T1(g)

15 B > 15 B'
x

= 10 Dq
15 B

15 B'
x

T1(g)
T2(g)

A2(g)

6 Dq
2 Dq

10 Dq

T1

d7 tetrahedral complex

[CoCl4]2-

Calculating B' and x

x
A

15 B'

T2

A2

T1

6 Dq
2 Dq

25 000

20 000

15 000

10 000 5 000

v / cm-1

10 Dq

1 = 3 300 cm-1

IR region

2 = 5 800 cm-1

visible

3 = 15 000 cm-1

visible

Racah Parameters
Free ion [Co2+]: B = 971 cm-1
[Co(H2O)6]2+

[CoCl4]2-

d7 octahedral complex

d7 tetrahedral complex

15 B' = 13 800 cm-1

15 B' = 10 900 cm-1

B' = 920 cm-1

B' = 727 cm-1

B' = 0.95
B

B' = 0.75
B

Nephelauxetic ratio,

is a measure of the decrease in electron-electron repulsion on complexation

The Nephelauxetic Effect

cloud expanding

- some covalency in M-L bonds M and L share electrons

- effective size of metal orbitals increases
- electron-electron repulsion decreases
Nephelauxetic series of ligands
F- < H2O < NH3 < en < [oxalate]2- < [NCS]- < Cl- < Br- < INephelauxetic series of metal ions
Mn(II) < Ni(II) Co(II) < Mo(II) > Re (IV) < Fe(III) < Ir(III) < Co(III) < Mn(IV)

Orgel Diagram, d5 oct and tet

T2(g)

50 000

T1(g)

A2(g)

40 000

Energy (cm-1)

T1(g)

E(g)
4
T2(g)
4

30 000

P
4
G
4

E(g), 4A1(g)

20 000

T2(g)

T1(g)

10 000

A1(g)

500

1000

Ligand Field Strength, Dq (cm-1)

Multiple absorption bands

d5 octahedral complex

Very weak intensity

[Mn(H2O)6]2+

Transitions are forbidden

0.03

Eg (G)

A1g (G)
T2g (D)

0.02

Eg (D)

T1g(G)
T2g (G)

0.01

v / cm-1
20 000

25 000

30 000

Spin Selection Rule

S = 0
There must be no change in spin multiplicity during an electronic transition

Laporte Selection Rule

l = 1
There must be a change in parity during an electronic transition
g u

Selection rules determine the intensity of electronic transitions


0.03

[Ti(OH2)6]3+, d1, Oh field

0.02

0.01

Spin allowed

- / cm-1

Laporte forbidden

10 000

20 000

30 000

Transition between d orbitals

Eg

D
T2g

oct

[CoCl4]2-, d7 Td

600

[V(H2O)6]3+, d2 Oh

10

400
5

200

25 000 20 000 15 000 10 000 5 000

v / cm-1

30 000

20 000

10 000

Spin allowed; Laporte forbidden

4

A2g

T1g

T2g

T2g

T1g

T1g

A2g

T1

T1

T2

A2

T1

T1g

T1
T2

A2

d7 tetrahedral

0
Dq

d2 octahedral

cm-1

Intensitas Warna
Intensitas warna suatu kompleks tergantung dari..

Aturan Seleksi

Transisi yang mengikuti aturan seleksi

transition disobeys selection rules

Transisi diizinkan (allowed)

Transisi terlarang (forbidden)

1.

Laporte Selection Rule

2.

Spin Selection Rule

Aturan Seleksi Laporte

Harus ada perubahan notasi paritas

s-orbital
gerade

e.g.

d-orbital
gerade

p-orbital
ungerade

p-orbital ke d-orbital

diizinkan menurut aturan seleksi Laporte

d-orbital ke d-orbital

terlarang menurut aturan seleksi Laporte

Transisi antar orbital-d (g) terlarang menurut aturan seleksi Laporte

Kompleks Oktahedral
Centrosymmetric: orbital-orbital t2g dan eg
Transisi d-d terlarang menurut aturan seleksi Laporte

Tetrahedral complexes
non-Centrosymmetric: orbital t2 dan e
aturan seleksi Laporte tidak teraplikasi

Komplek tetrahedral biasanya memiliki warna yang lebih kuat dari pada komplek
analog oktahedral

Aturan Seleksi Spin

Tidak boleh ada perubahan Spin

allowed

S = 0
forbidden

Relaxation of the Laporte Selection Rule for Tetrahedral Complexes

Octahedral complex
Centrosymmetric
Laporte rule applies

Tetrahedral complex
Non-centrosymmetric
Laporte rule relaxed

inversion
centre

Orbital mixing:

Oh complex

d eg and t2g

p t1u

Td complex

d e and t2

p t2

In tet complexes, d-orbitals have some p character

Intenstity of transitions in d5 complexes

Laporte forbidden

Energy (cm-1)
4

50 000

T2(g)

Spin forbidden

T1(g)
4
A2(g)
4

40 000

T1(g)
4
E(g)
4
T2(g)
4
E(g), 4A1(g)
4

30 000
4
4

P
G

20 000

T2(g)

T1(g)

10 000

A1(g)

500

1000

Dq (cm-1)

Weak transitions occur due to:

Unsymmetrical Vibrations (vibronic transitions)

Spin-orbit Coupling

Selection Rules
S = 0

Spin Selection Rule

There must be no change in spin multiplicity during an electronic transition

l = 1

Laporte Selection Rule

There must be a change in parity during an electronic transition

Relaxation of Selection Rules

Tetrahedral complexes: non-centrosymmetric
Laporte rule relaxed by orbital mixing
Octahedral complexes: centrosymmetric
Laporte rule relaxed by vibronic coupling
d5 complexes:

vibronic coupling and Spin-orbit coupling

Selection Rules
Transition

complexes

Spin forbidden
Laporte forbidden

10-3 1

Many d5 Oh cxs
[Mn(OH2)6]2+

1 10

Many Oh cxs
[Ni(OH2)6]2+

10 100

Some square planar cxs

[PdCl4]2-

100 1000

6-coordinate complexes of low symmetry,

many square planar cxs particularly with
organic ligands

102 103

Some MLCT bands in cxs with unsaturated ligands

102 104

Acentric complexes with ligands such as acac, or

with P donor atoms

103 106

Many CT bands, transitions in organic species

Spin allowed
Laporte forbidden

Spin allowed
Laporte allowed

Broadening

0.03

1. Molecular vibration

0.02

Eg (G)

A1g (G)
4
T2g (D)

T1g(G)

Eg (D)

T2g (G)

Energy (cm )
-1

50 000
4

T2g

T1g

0.01

20 000

v / cm-1

A2g

25 000

40 000
4
4

E
T
E , A1g

4
4 g
2g
4
4
g

30 000
4
4

T1g

P
G

Eg

T2g

20 000

T1g

T2g

10 000

E
T1g
6
A1g

A1g

6
6

500

1000

Dq (cm )
-1

Dq

30 000

Broadening

[Ni(H2O)6]2+, d8
spin forbidden transition

2. Spin-Orbit Coupling
MS- MS

T1g 3A2g

10

> ML - MS > ML - MS

14 000

25 000

50 000
- / cm-1

E/B

[Ni(H2O)6]2+, d8

Coupling between an allowed and

T1g

Eg

T2g

forbidden transition which are very

close in energy

A2g

Dq/B

3. The Jahn-Teller Theorum: Any non-linear molecule in a degenerate electronic

state will undergo distortion to lower it's symmetry and lift the degeneracy
Degenerate electronic ground state:

T or E

Non-degenerate ground state:

A
d3
d5 (high spin)
d6 (low spin)
d8

B1g

2
2

Eg

A2g
6
A1g
1
A1g
3
A2g
4

[Ti(H2O)6]3+, d1

A1g

T2g
10 000

20 000

30 000

- / cm-1

The Spectrochemical Series

eg

eg

I- < Br- < S2- < SCN- < Cl-< NO3- < F- < OH- < ox2-

t 2g

< H2O < NCS < CH3CN < NH3 < en < bpy
-

< phen < NO2- < phosph < CN- < CO

t 2g

weak field ligands

strong field ligands

e.g. H2O

e.g. CN-

high spin complexes

low spin complexes

The Spin Transition

d5
4

T2g

Tanabe-Sugano diagrams

A1g

E/B

T1g
4
Eg
4
T2g

All terms included

A1g, 4E
2
A1g
2
T1g

Higher levels drawn relative to GS

T2g
2
Eg

High-spin and low-spin configurations

A2g, 2T1g

T2g

Ground state assigned to E = 0

Energy in terms of B

Critical value of

A1g
4
T1g
6

WEAK FIELD

/B

T2g

STRONG FIELD

10

Tanabe-Sugano diagram for d2 ions

[V(H2O)6]3+: Three spin allowed transitions

E/B
30 000

20 000

1 = 17 800 cm-1

visible

2 = 25 700 cm-1

visible

10 000

cm-1

3 = obscured by CT transition in UV

25 700 =

1.44

/B

17 800
3 = 2.1 1 = 2.1 x 17 800
3 = 37 000 cm-1
/B = 32

32

A2g

1 = 17 800 cm-1

T1g

2 = 25 700 cm-1

T2g

10 Dq

3 = 37 000 cm-1

= 3 1
= 19 200 cm-1

2 Dq
3

F
6 Dq
x
T1g

o / B

32

600 cm-1

E/B
1 = 17 800 cm-1
2 = 25 700 cm-1
2

E/B = 43 cm-1

E/B = 30 cm-1

E/B = 43 cm-1

E = 25 700 cm-1

600 cm-1

o / B

32

19 200 cm-1

/B = 32

Calculating 3

1 = 17 400 cm-1
2 = 24 500 cm-1

E/B

When

1 = E =17 400 cm-1

E/B = 24

so

B = 725 cm-1

When

2 = E =24 500 cm-1

E/B = 34

so

E/B = 34 cm-1
E/B = 24 cm-1

B = 725 cm-1

If /B = 24
= 24 x 725 = 17 400 cm-1

/B = 24

Energy diagram for octahedral d complex

3

T1g

15 B'

T2g

A2g

2 = 24 500 cm-1

visible

For Oh d3, o = 1 = 17 400 cm-1

T1g

visible

3 = obscured by CT transition

1 = 17 400 cm-1

6 Dq

o / B = 24

2 Dq
B = 725 cm-1
10 Dq

d0 and d10 ions

Zn2+

d10 ion

d0 and d10 ion have no d-d transitions

white

TiF4

d0 ion

white

TiCl4

d0 ion

white

TiBr4

d0 ion

TiI4

d0 ion

orange
dark brown

[MnO4]-

Mn(VII)

d0 ion extremely purple

[Cr2O7]-

Cr(VI)

d0 ion

bright orange

[Cu(MeCN)4]+

Cu(I)

d10 ion

colourless

[Cu(phen)2]+

Cu(I)

d10 ion

dark orange

Charge Transfer Transitions

Metal-to-ligand charge transfer

Ligand-to-metal charge transfer

MLCT transitions

LMCT transitions
Charge Transfer Transitions

d-d transitions
eg*

t2g*
Md
L

Selection rules
CT transitions are spin allowed and Laporte allowed

Transitions

occur

from

singlet GS to a singlet ES
S = 0

Transitions occur between

metal based orbitals with dcharacter and ligand based
orbitals with p-character
l = 1

CT transitions are therefore much more intense than d-d transitions

LMCT Transitions

O
Mn
O

spin-allowed; Laporte allowed

O
O

[MnO4]-, dark purple

LMCT = ligand to metal charge transfer

e- rich ligand
-

- -

O , Cl , Br , I
2-

e- poor metal (electropositive), high charge

Cr(III), d3 ion, Mn(VII), d0 ion

MO diagram of MnO4-

ML4

4L

t*
(n+1)p
(n+1)s

nd

t2

L(t1) M(e)

17 700 cm-1

L(t1) M(t2*)

29 500 cm-1

L(t2) M(e)

30 300 cm-1

L(t2) M(t2*)

44 400 cm-1

a1*
a1

e, t2

t2*

t1

t1 ,t2

t2
a1 ,t2
t2
a1

spin-allowed; Laporte allowed

LMCT Transitions
[CrCl(NH3)5]2+, Cr(III), d3

NH3

H3N

Cr

H3N

LMCT

2+
NH3
Cl

log(/L mol-1 cm-1)

H3N
4
3
2

d-d

d-d

200
(50 000 cm-1)

400
(25 000 cm-1)

600
nm
-1
(17 000 cm )

Identifying charge transfer transitions

Intensity
Solvatochromism - variation in absorption wavelength with solvent

Charge-Transfer Transitions: MLCT

+
N

spin-allowed; Laporte allowed

500
400

Cu
N

300

max = 458 nm

200

[Cu(phen)2] , dark orange

100

400

500

600

nm

MLCT = metal to ligand charge transfer

e- rich metal, low charge, lower OS

-acceptor ligand with low-lying * orbitals

Cu(I), d10 ion

1,10-phenanthroline

Charge-Transfer Transitions: MLCT

2+

spin-allowed; Laporte allowed

- *

N
N

max = 452 nm
MLCT

Ru N
N
N

[Ru(bpy)3]2+, bright orange

200

300

400

500

nm

MLCT = metal to ligand charge transfer

e- rich metal, low charge, lower OS

-acceptor ligand with low-lying * orbitals

Ru(II), d6 ion, low spin

2,2'-bipyridine

 Interelectron repulsion

Limits of LFT existence of electronic states

Russel-Saunders coupling

Collecting microstates into terms

Using Hund's rules GS and ES with same multiplicity

Effect of LF on free ion terms

Orgel diagram for d1, d4, d6, d9 ions

[Ti(OH2)6]3+

Orgel diagram for d2, d3, d7, d8 ions

[Ni(OH2)6]2+

Calculating , x and B'

[Co(OH2)6]2+, [CoCl4]2-

Racah parameters in free ions and complexes

The Nephelauxetic effect
Orgel diagram for d5 ions

Spin and Laporte Selection Rules

[Mn(OH2)6]2+

Selection rules for Oh and Td complexes

Lifting selection rules
Origin of band broadening

Tanabe-Sugano diagrams

Low spin complexes

Calculating E, B' and

CT transitions

LMCT

[Ni(OH2)6]2+, [Mn(OH2)6]2+, [Ti(OH2)6]3+

[Mn(CN)6]4[Cr(OH2)6]3+, [V(OH2)6]3+

[CoCl(NH3)5]2+, [MnO4]-

Menghitung oct menggunakan T-S. misal: d2, V(H2O)63+

Spekturm teramati
17,800 cm-1
2: 25,700 cm-1
Cara: cocokan energi yang teramati ke diagram.
Kemudian cari nilai splitting parameter, o/B, yang
memberikan dua eksitasi dengan ratio 25,700/17,800 =
1.44

E/B

Pertama, jelas 1 merujuk pada 3T1 3T2

2 bisa 3T1 3A2 atau 3T1 3T1.
Rasio 2/1 = 1.44 dihasilkan pada o / B= 31
O/B

Energi eksitasi
Untuk 1: E/B = 17,800 cm-1 /B = 29 menghasilkan
B = 610 cm-1
menggunakan 31 = o/B = o/610 didapat
o = 19,000 cm-1

Menentukan o dari spektra d3

mixing

mixing

Lowest energy transition = o

Spektrum elektronik [Ni(H2O)6]2+:

Komplex terlihat berwarna hijau, karena menyerap sangat lemah pada 500 nm,
Panjang gelombang dari cahaya hijau

UV

visible

infrared
[Ni(H2O)6]2+

A2g 1Eg

Hijau

A2g 3T2g

Aturan Seleksi
(menentukan intensitas serapan)
Laporte rule
g g forbidden (transition d-d forbidden)
Tetapi g u allowed (transition d-p allowed)

Spin rule
Transition antara keadaan multipisiti berbeda forbidden
Transition antara keadaan multipisiti yang sama allowed