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Spectra of Complexes

The document discusses electronic spectra of transition metal complexes. It provides examples of calculating term symbols and microstates for electron configurations like d2 and d3. It also summarizes Tanabe-Sugano diagrams, selection rules, and charge transfer transitions. An example calculates the ligand field splitting parameter (Dq) and Racah interelectronic repulsion parameter (B) for [CoF6]-4 using its absorption bands.

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Sheena Gagarin
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64 views41 pages

Spectra of Complexes

The document discusses electronic spectra of transition metal complexes. It provides examples of calculating term symbols and microstates for electron configurations like d2 and d3. It also summarizes Tanabe-Sugano diagrams, selection rules, and charge transfer transitions. An example calculates the ligand field splitting parameter (Dq) and Racah interelectronic repulsion parameter (B) for [CoF6]-4 using its absorption bands.

Uploaded by

Sheena Gagarin
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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The Electronic Spectra

of Complexes
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
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 centro-symmetric environments,
transitions can only occur between states of
opposite parity ( u -> g; g -> u)
– allowed
• d --> p; s --> p
• intense lines;   
– forbidden
• d --> d; s -->d
• weak line;  
Other Observed Transitions
• Non-bonding to antibonding
– in octahedral symmetry
– t2 e*
• weak line;  
– in tetrahedral symmetry
–e t2*
• weak line;  
d 2 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
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
2  4T => 21,550 cm-1
2

o/B = 21,550/B = 32.8


B = 657 cm-1

32.8
EXAMPLE:Calculate Dq
-4
and B for [CoF6] .
d7 case
absorption bands:
– 7.15 kK 1 = 4T1g -> 4T2g

– 15.2 2 = 4T1g -> 4T2g

– 19.2 3 = 4T1g(F) -> 4T1g(P)


EXAMPLE:Calculate Dq
-4
and B for [CoF6] .
d7 case absorption bands:
– 7.15 kK 1 = 4T1g -> 4T2g
– 15.2 2 = 4T1g -> 4T2g
– 19.2 3 = 4T1g(F) -> 4T1g(P)

1 = 8Dq + c = 7.15 kK
2 = 18Dq + c = 15.2 kK
3 = 15B + 6Dq + 2c = 19.2 kK
EXAMPLE:Calculate Dq
-4
and B for [CoF6] .
d7 case absorption bands:
1 = 7.15 kK 2 = 15.2 3 = 19.2
1 = 8Dq + c = 7.15 kK
2 = 18Dq + c = 15.2 kK
3 = 15B + 6Dq + 2c = 19.2 kK
2 - 1 = 10Dq
= (15.2 - 7.2)kK = 8.0 kK
EXAMPLE:Calculate Dq
-4
and B for [CoF6] .
d7 case absorption bands:
1 = 7.15 kK 2 = 15.2 3 = 19.2
1 = 8Dq + c = 7.15 kK
2 = 18Dq + c = 15.2 kK
3 = 15B + 6Dq + 2c = 19.2 kK
2 - 1 = 10Dq
= (15.2 - 7.2)kK = 8.0 kK
Dq = 0.80 kK
EXAMPLE:Calculate Dq
-4
and B for [CoF6] .
d7 case absorption bands:
1 = 8Dq + c = 7.15 kK
2 = 18Dq + c = 15.2 kK
3 = 15B + 6Dq + 2c = 19.2 kK
Dq = 0.80 kK
from 1
c = 1 - 8Dq
= (7.15 - 8(0.80))kK = 0.8 kK
EXAMPLE:Calculate Dq
and B for [CoF6]-4.
d7 case absorption bands:
1 = 8Dq + c = 7.15 kK
2 = 18Dq + c = 15.2 kK
3 = 15B + 6Dq + 2c = 19.2 kK
Dq = 0.80 kK
from 2
c = 2 - 18Dq
= (15.2 - 18(0.80))kK = 0.8 kK
EXAMPLE:Calculate Dq
-4
and B for [CoF6] .
d7 case absorption bands:
1 = 8Dq + c = 7.15 kK
2 = 18Dq + c = 15.2 kK
3 = 15B + 6Dq + 2c = 19.2 kK
Dq = 0.80 kK; c = 0.80 kK
15B = 3 - 6Dq - 2c
B = (3 - 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   
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   
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

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