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Warna senyawa kompleks

Analisis spektra UV-Vis


senyawa kompleks

Konfigurasi elektronik atom multi-elektron

Apakah makna konfigurasi 2p2 ?

n = 2; l = 1; ml = -1, 0, +1; ms = ± 1/2

Penataan elektron yang sesuai

microstates
beda energi karena tolakan antar elektron (inter-electronic repulsions)

Konfigurasi elektronik atom multi-elektron Æ pasangan RS Menentukan microstates untuk p2


Russell-Saunders (or LS) coupling

Untuk tiap atom multi-elektron


Untuk tiap elektron 2p L = total orbital angular momentum quantum number
n = 2; l = 1 S = total spin angular momentum quantum number
ml = -1, 0, +1 Spin multiplicity = 2S+1
ms = ± 1/2
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

1
Menentukan harga L, ML, S, Ms untuk terms yang berbeda

1S

Spin multiplicity = 2S + 1
2P

Mengklasifikasikan microstates p2

Next largest ML is +1,


Largest ML is +2,
so L = 1 (a P term)
so L = 2 (a D term)
Largest ML is +2, and MS = 0, ±1 for ML = +1,
and MS = 0 for ML = +2,
so L = 2 (a D term) 2S +1 = 3
2S +1 = 1 (S = 0) 3P
and MS = 0 for ML = +2, 1D
2S +1 = 1 (S = 0) ML is 0, L = 0
1D
2S +1 = 1
1S

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,
Spin multiplicity = # columns of microstates 2S +1 = 1
1S

Energy of terms (Hund’s rules)

Lowest energy (ground term)


Highest spin multiplicity
3P term for p2 case

3P has S = 1, L = 1

If two states have


the same maximum spin multiplicity
Ground term is that of highest L

2
single e- (electronic state) Æ multi-e- (atomic state)
before we did:

p2

ML & MS the largest MLÆ L


spin multiplicity = Σcolumns
or 2S+1, S the largest MS
Microstate
Table
States (S, P, D)
Spin multiplicity

Terms
3P, 1D, 1S

Ground state term


3P

For metal complexes we need to consider


d1-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…

Transitions between electronic terms will give rise to spectra

3
Remember what we’re after ? Selection rules
(determine intensities)

Laporte rule
Theory to explain electronic g → g forbidden (that is, d-d forbidden)
excitations/transitions observed for metal but g → u allowed (that is, d-p allowed)

complexes
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

Breakdown of selection rules Group theory analysis of term splitting

Free ion
term for
d2

3F, 3P, 1G, 1D, 1S

Real complexes

4
Tanabe-Sugano diagrams d2 complex: Electronic transitions and spectra

• show correlation of
spectroscopic transitions
observed for ideal Oh
complexes with electronic
states only 2 of 3 predicted transitions
• energy axes are observed
parameterized in terms of ∆o
and the Racah parameter (B)
which measures repulsion d2
between terms of the same
multiplicity

TS diagrams Other dn configurations Other configurations

d3
d1 d9

d2 d8
d3
The limit between
high spin and low spin

the spectra of dn hexaaqua complexes of 1st row TMs


The d5 case

All possible transitions forbidden


Very weak signals, faint color

5
symmetry labels

Charge transfer spectra


Metal character

LMCT

Ligand character

Ligand character

MLCT
Metal character

Much more intense bands

6
[Cr(NH3)6]3+

Determining ∆o from spectra Determining ∆o from spectra


mixing

d1 d9

mixing

One transition allowed of energy ∆o Lowest energy transition = ∆o

Ground state mixing

E (T1g→A2g) - E (T1g→T2g) = ∆o