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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
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
Nephelauxetic ratio, b
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
t
2g
weak field ligands strong field ligands
e.g. H O e.g. CN-
2
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
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
24 500 = 1.41
17 400
D/B = 24
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
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
32.8
EXAMPLE:Calculate Dq and B
for [CoF6]-4.
d7 case
absorption bands:
– 7.15 kKn1 = 4T1g -> 4T2g
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
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
d-d transitions
Lp*
e *
g
t *
2g
Md
Lp
Ls
Absorption Spectrum of [CrCl(NH3)5]+2
d3 case