uv vis spektra senyawa kompleks2 penting
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Analisis spektra UV-Vis senyawa kompleks
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Warna senyawa kompleks
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Konfigurasi elektronik atom multi-elektron
Apakah makna konfigurasi 2p2 ?
n = 2; l = 1; ml = -1, 0, +1; ms = ± 1/2
Penataan elektron yang sesuai
microstatesbeda energi karena tolakan antar elektron (inter-electronic repulsions)
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Konfigurasi elektronik atom multi-elektron pasangan RS
Russell-Saunders (or LS) coupling
Untuk tiap elektron 2p n = 2; l = 1
ml = -1, 0, +1ms = ± 1/2
Untuk tiap atom multi-elektronL = total orbital angular momentum quantum numberS = total spin angular momentum quantum number
Spin multiplicity = 2S+1
ML = ∑ml (-L,…0,…+L)MS = ∑ms (S, S-1, …,0,…-S)
• ML/MS menyatakan microstates • L/S menyatakan states (kumpulan microstates)• Group microstates dengan energi yang sama disebut terms
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Menentukan microstates untuk p2
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Spin multiplicity = 2S + 1
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Menentukan harga L, ML, S, Ms untuk terms yang berbeda
1S
2P
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Mengklasifikasikan microstates p2
Spin multiplicity = # columns of microstates
Next largest ML is +1,so L = 1 (a P term)
and MS = 0, ±1 for ML = +1,2S +1 = 3
3P
One remaining microstate ML is 0, L = 0 (an S term)
and MS = 0 for ML = 0,2S +1 = 1
1S
Largest ML is +2,so L = 2 (a D term)
and MS = 0 for ML = +2,2S +1 = 1 (S = 0)
1D
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Largest ML is +2,so L = 2 (a D term)
and MS = 0 for ML = +2,2S +1 = 1 (S = 0)
1D
Next largest ML is +1,so L = 1 (a P term)
and MS = 0, ±1 for ML = +1,2S +1 = 3
3P
ML is 0, L = 0 2S +1 = 1
1S
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Energy of terms (Hund’s rules)
Lowest energy (ground term)Highest spin multiplicity
3P term for p2 case
If two states havethe same maximum spin multiplicity
Ground term is that of highest L
3P has S = 1, L = 1
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before we did:
p2
ML & MS
MicrostateTable
States (S, P, D)Spin multiplicity
Terms3P, 1D, 1S
Ground state term3P
the largest ML Lspin multiplicity = Σcolumnsor 2S+1, S the largest MS
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single e- (electronic state) multi-e- (atomic state)
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For metal complexes we need to considerd1-d10
d2
3F, 3P, 1G, 1D, 1S
For 3 or more electrons, this is a long tedious process
But luckily this has been tabulated before…
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Transitions between electronic terms will give rise to spectra
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Remember what we’re after ?
Theory to explain electronic excitations/transitions observed for metal complexes
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Selection rules(determine intensities)
Laporte rule
g g forbidden (that is, d-d forbidden)
but g u allowed (that is, d-p allowed)
Spin rule
Transitions between states of different multiplicities forbidden
Transitions between states of same multiplicities allowed
These rules are relaxed by molecular vibrations, and spin-orbit coupling
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Breakdown of selection rules
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Group theory analysis of term splitting
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Free ion term for d2
3F, 3P, 1G, 1D, 1S
Real complexes
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Tanabe-Sugano diagrams
d2
• show correlation of spectroscopic transitions observed for ideal Oh complexes with electronic states
• energy axes are parameterized in terms of Δo and the Racah parameter (B) which measures repulsion between terms of the same multiplicity
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d2 complex: Electronic transitions and spectra
only 2 of 3 predicted transitions observed
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TS diagrams Other dn configurations
d1 d9
d3
d2 d8
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d3
Other configurations
The limit betweenhigh spin and low spin
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the spectra of dn hexaaqua complexes of 1st row TMs
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The d5 case
All possible transitions forbiddenVery weak signals, faint color
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symmetry labels
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Charge transfer spectra
LMCT
MLCT
Ligand character
Metal character
Metal character
Ligand character
Much more intense bands
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[Cr(NH3)6]3+
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Determining o from spectra
d1d9
One transition allowed of energy o
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Lowest energy transition = o
mixing
mixing
Determining o from spectra
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Ground state mixing
E (T1gA2g) - E (T1gT2g) = o