spectrum d 3 [Cr(NH3)3 ] +3

Term Symbols
sejumlah cara yang berbeda elektron dapat
ditempatkan dalam himpunan situs orbital

Spectroscopic Term Symbols

n!
# microstates = --------
e! h!
dimana n => max # jumlah e-dalam sublevel
(jumlah e + h)
e => #e-
h => #"holes" ( yg tidak ditempati e-)
Contoh: p2
2 electrons dlm orbital p

n!
# microstates = --------
e! h!

6! 5*6
= ------ = ---------
2!*4! 1*2
= 15
Contoh : p2
2 electrons in a p orbital
term symbols => 2S + 1L
ground state => S tertinggi
L tertinggi
Contoh: p2 case
2 electrons in a p orbital

L
+1
0
-1
S

s = +1/2 s = -1/2
1D Term Microstates
1D L
+2 +1 0 -1 -2

S 0 0 0 0 0
1S Term Microstate

1S L
0

S 0
3P Term Microstates

3P L
+1 0 -1
+1
S 0
-1

thus, ground state is the 3P term

Example: p2 case
2 electrons in a p orbital
the various terms for p and d electron combinations
J=|L + S|
therefore, 3P term has
J = 2, 1, or 0 3P 3P 3P
2 1 0
J Values
number of J values:
S < L2S + 1 values of J
L < S 2L + 1 values of J
Hund's Third Law
ground state lowest J for less than 1/2 filled shell
highest J for more than 1/2 filled shell
Atomic Term Symbols
L= 0 1 2 3 4 5 6
S P D F G H I
Selection Rules
allowed
ground and excited states for a possible transition
possess the required characteristics
forbidden
ground and excited states for a possible transition
do not possess the required characteristics
Selection Rules
selection rules are based on idealized theoretical
models
some forbidden transitions appear in real spectra
because the real molecule does not fit the
idealized theoretical model
LaPortes Rule
in centrosymmetric environments, transitions can
only occur between states of opposite parity ( u ->
g; g -> u)
allowed
d --> p; s --> p
intense lines; e
forbidden
d --> d; s -->d
weak line; e-
Other Observed Transitions
Non-bonding to antibonding
in octahedral symmetry
t2 e*
weak line; e-
in tetrahedral symmetry
e t2*
weak line; e-
Transition e complexes

Spin forbidden 10-3 1 Many d5 O cxs

Laporte forbidden [Mn(OH ) h]2+
26
Spin allowed
Laporte forbidden 1 10 Many O cxs
[Ni(OH h) ]2+
26
10 100 Some square planar cxs
[PdCl ]2-
4
100 1000 6-coordinate complexes of low symmetry,
many square planar cxs particularly with
organic ligands

Spin allowed 102 103 Some MLCT bands in cxs with unsaturated
ligands
Laporte allowed
102 104 Acentric complexes with ligands such as acac, or
with P donor atoms

103 106 Many CT bands, transitions in organic species

Term
S = +1/2 S = -1/2
L=2
L=1
L=0
L = -1
L= -2
d 2 Case
10! 9*10
#microstates = ---------- = ---------- = 45
2!*8! 2
d 2 Configuration
Term Number of States
1G 9x1 = 9
3F 7x3 = 21
1D 5x1 = 5
3P 3x3 = 9
1S 1x1 = 1
Total = 45
Konfigurasi Keadaan dasar Term yg lain
d1 dan d9 2D
d2 dan d8 3F 3P, 1G, 1D, 1S
d3 dan d7 4F 4P,3H, 2G, 2F, 2D, 2P
d4 dan d6 5D 3H, 3G, 3F,3D, 3P,
1I,1G,1F,1D,1S
d5 6S 4G,4F,4D,4P,2I,2H,2G,2F, 2D,
2P,2S
d10 1S
Correlation Diagram for d 1
d2 Configuration
Dr. S. M. Condren
Noncrossing Rule
Racah Parameters

Free ion [Co2+]: B = 971 cm-1

[Co(H O) ]2+ [CoCl ]2-

2 6 4

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' = 0.75

B B

Nephelauxetic ratio, b

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

 cloud expanding
The Nephelauxetic Effect

- 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- < H O < NH < en < [oxalate]2- < [NCS]- < Cl- < Br- < I-
2 3
Nephelauxetic series of metal ions

Mn(II) < Ni(II) Co(II) < Mo(II) > Re (IV) < Fe(III) < Ir(III) < Co(III) < Mn(IV)
 The Spectrochemical Series
e
g

e
g I- < Br- < S2- < SCN- < Cl-< NO - < F- < OH- < ox2-
D 3
D
t
2g < H O < NCS- < CH CN < NH < en < bpy
2 3 3

< phen < NO - < phosph < CN- < CO

2

t
2g
weak field ligands strong field ligands
e.g. H O e.g. CN-
2

high spin complexes low spin complexes

The Spin Transition

 d5 Tanabe-Sugano diagrams
4T
2g

2A
1g
E/B
4T
1g All terms included
4E
g
4T Ground state assigned to E = 0
2g
4A 4E
1g,
Higher levels drawn relative to GS
2A
2T
1g Energy in terms of B
1g
High-spin and low-spin configurations
2T
2g
2E
g

4A 2T Critical value of D
2g, 1g

4T
2g

6A
1g
4T
1g

2T
2g

WEAK FIELD D/B STRONG FIELD

 10
Tanabe-Sugano diagram for d2 ions
e
[V(H O) ]3+: Three spin allowed transitions
2 6 5

E/B

30 000 20 000 10 000

-
n /cm-1

n = 17 800 cm-1 visible

1
n = 25 700 cm-1 visible
2
n = obscured by CT transition in UV
3

25 700 = 1.44 D/B = 32

17 800

n = 2.1n = 2.1 x 17 800

3 1
n = 37 000 cm-1
3
D/B = 32
 E/B

n = 17 800 cm-1
1
n = 25 700 cm-1
2

n
E/B = 43 cm-1 2

E/B = 30 cm-1 n
1

E/B = 43 cm-1 E = 25 700 cm-1

B = 600 cm-1
D /B = 32
o
D = 19 200 cm-1
o D/B = 32
Tanabe-Sugano diagram for d3 ions n = 17 400 cm-1 visible
1
[Cr(H O) ]3+: Three spin allowed transitions n = 24 500 cm-1 visible
2 6 2
n = obscured by CT transition
E/B 3

24 500 = 1.41
17 400

D/B = 24

n = 2.1n = 2.1 x 17 400

3 1
n = 36 500 cm-1
3

D/B = 24
 Calculating n n = 17 400 cm-1
3 1
n = 24 500 cm-1
2
E/B
When n = E =17 400 cm-1
1
E/B = 24
so B = 725 cm-1

When n = E =24 500 cm-1

2
E/B = 34
so B = 725 cm-1
E/B = 34 cm-1

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

D/B = 24
d0 and d10 ions d0 and d10 ion have no d-d transitions

Zn2+ d10 ion white

TiF d0 ion white

4
TiCl d0 ion
4 white
TiBr d0 ion
4 orange
TiI d0 ion
4 dark brown

[MnO ]- Mn(VII) d0 ion extremely purple

4
[Cr O ]- Cr(VI) d0 ion bright orange
2 7

[Cu(MeCN) ]+ Cu(I) d10 ion colourless

4
[Cu(phen) ]+ Cu(I) d10 ion dark orange
2

Charge Transfer Transitions

d 3 [Cr(NH3)3 +3
] spectrum

28,500 cm-1 21,550 cm-1 28,500

= 1.32
21,550
d2, d3, d7, and d8 Octahedral and
Tetrahedral with Bending
 Tanabe-Sugano
diagram for d2
configuration
4A 4T => 21,550 cm-1
2 2

Do/B = 21,550/B = 32.8

B = 657 cm-1

32.8
EXAMPLE:Calculate Dq and B
for [CoF6]-4.
d7 case
absorption bands:
7.15 kK n1 = 4T1g -> 4T2g

15.2 n2 = 4T1g -> 4T2g

19.2 n3 = 4T1g(F) -> 4T1g(P)

EXAMPLE:Calculate Dq and B
-4
for [CoF6] .
d7 case absorption bands:
7.15 kK n1 = 4T1g -> 4T2g
15.2 n2 = 4T1g -> 4T2g
19.2 n3 = 4T1g(F) -> 4T1g(P)

n1 = 8Dq + c = 7.15 kK
n2 = 18Dq + c = 15.2 kK
n3 = 15B + 6Dq + 2c = 19.2 kK

Dr. S. M. Condren
EXAMPLE:Calculate Dq and B
for [CoF6]-4.
d7 case absorption bands:
n1 = 7.15 kK n2 = 15.2 n3 = 19.2
n1 = 8Dq + c = 7.15 kK
n2 = 18Dq + c = 15.2 kK
n3 = 15B + 6Dq + 2c = 19.2 kK
n2 - n1 = 10Dq
= (15.2 - 7.2)kK = 8.0 kK
EXAMPLE:Calculate Dq and B
for [CoF6]-4.
d7 case absorption bands:
n1 = 7.15 kK n2 = 15.2 n3 = 19.2
n1 = 8Dq + c = 7.15 kK
n2 = 18Dq + c = 15.2 kK
n3 = 15B + 6Dq + 2c = 19.2 kK
n2 - n1 = 10Dq
= (15.2 - 7.2)kK = 8.0 kK
Dq = 0.80 kK
EXAMPLE:Calculate Dq and B
for [CoF6]-4.
d7 case absorption bands:
n1 = 8Dq + c = 7.15 kK
n2 = 18Dq + c = 15.2 kK
n3 = 15B + 6Dq + 2c = 19.2 kK
Dq = 0.80 kK
from n1
c = n1 - 8Dq
= (7.15 - 8(0.80))kK = 0.8 kK
EXAMPLE:Calculate Dq and B for
[CoF6]-4.
d7 case absorption bands:
n1 = 8Dq + c = 7.15 kK
n2 = 18Dq + c = 15.2 kK
n3 = 15B + 6Dq + 2c = 19.2 kK
Dq = 0.80 kK
from n2
c = n2 - 18Dq
= (15.2 - 18(0.80))kK = 0.8 kK
 EXAMPLE:Calculate Dq and B
for [CoF6]-4.
d7 case absorption bands:
n1 = 8Dq + c = 7.15 kK
n2 = 18Dq + c = 15.2 kK
n3 = 15B + 6Dq + 2c = 19.2 kK
Dq = 0.80 kK; c = 0.80 kK
15B = n3 - 6Dq - 2c
B = (n3 - 6 Dq - 2c)/15
= (19.2 kK - 6(0.80kK) - 2(0.80kK))/15 = 0.85 kK
The Jahn-Teller Distortion: 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 4A
d5 (high spin) 6A2g
d6 (low spin) 1A1g
d8 3A1g
2g

2B
1g A
2E [Ti(H O) ]3+, d1
g 2 6
2A
1g

2T
2g
-
n / cm-1
10 000 20 000 30 000
Spectra of [Co(en)3]-3 and [Co(ox)3]-3

Complex n n2 n-n2
A A A
[Co(ox)3]-3 6061 4202 13699
[Co(en)3]-3 4673 3390 12346
Spectra of [Co(en)3]-3 and [Co(ox)3]-3

Complex n n2 n-n2
A A A
[Co(ox)3]-3 6061 4202 13699
[Co(en)3]-3 4673 3390 12346
d0 and d10 ions d0 and d10 ion have no d-d transitions

Zn2+ d10 ion white

TiF d0 ion white

4
TiCl d0 ion
4 white
TiBr d0 ion
4 orange
TiI d0 ion
4 dark brown

[MnO ]- Mn(VII) d0 ion extremely purple

4
[Cr O ]- Cr(VI) d0 ion bright orange
2 7

[Cu(MeCN) ]+ Cu(I) d10 ion colourless

4
[Cu(phen) ]+ Cu(I) d10 ion dark orange
2

Charge Transfer Transitions

A Summary of
the Charge
Transfer
Transitions in
an Octahedral
Complex
 Metal-to-ligand charge transfer Ligand-to-metal charge transfer
MLCT transitions LMCT transitions

Charge Transfer Transitions

d-d transitions
Lp*
e *
g

t *
2g

Md
Lp

Ls
Absorption Spectrum of [CrCl(NH3)5]+2

d3 case