Chapter 13

The Electronic Spectra of

Complexes
Fig 13.1 The spectrum of d3
[Cr(NH3)3]+3
 Spectroscopic Term Symbols
• microstates => number of different ways
e- can be placed in a given set of orbital sites
sejumlah cara yang berbeda elektron dapat
ditempatkan dalam himpunan situs orbital
•
 Spectroscopic Term Symbols
n!
# microstates = --------
e! h!
where n => max # e-s in sublevel
(sum of e + h)
e => #e- in case study
h => #"holes" in case study
(hole is a site not occupied by an e-)
Example: p2 case
2 electrons in a p orbital

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

6! 5*6
= ------ = ---------
2!*4! 1*2
= 15 (4! factors out)
Example: p2 case
2 electrons in a p orbital

L
+1
0
-1
S

s = +1/2 s = -1/2
Example: p2 case
2 electrons in a p orbital
term symbols => 2S + 1L
ground state => highest S
highest L
 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<L 2S + 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
 LaPorte’s 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-
 d2 Case
L
+2
+1
m 0
-1
-2
S

+1/2 -1/2
 Term
S = +1/2 S = -1/2
L=2
L=1
L=0
L = -1
L= -2
Konfigurasi Keadaan dasar Term yg lain
d1 dan d9 2D
d2 dan d9 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 d1
 d2 Case
10! 9*10
#microstates = ---------- = ---------- = 45
2!*8! 2
 d2 Configuration
Term Number of States
1G 9x1 = 9
3F 7x3 = 21
1D 5x1 = 5
3P 3x3 = 9
1S 1x1 = 1
Total = 45
d2 Configuration
Tanabe-Sugano
diagram for d2
configuration
Noncrossing Rule
Tanabe-Sugano
diagram for d2
configuration
d3 [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 kKn1 = 4T1g -> 4T2g

– 15.2 n2 = 4T1g -> 4T2g

– 19.2 n3 = 4T1g(F) -> 4T1g(P)

 EXAMPLE:Calculate Dq and B for
-4
[CoF6] .
d7 case absorption bands:
– 7.15 kKn1 = 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
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
A Summary of
the Charge
Transfer
Transitions in
an Octahedral
Complex
Absorption Spectrum of [CrCl(NH3)5]+2

d3 case