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# Warna senyawa kompleks

senyawa kompleks

## 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

## 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

3P

d1-d10

d2

## 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

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 d5 case

## All possible transitions forbidden

Very weak signals, faint color

5
symmetry labels

Metal character

LMCT

Ligand character

Ligand character

MLCT
Metal character

6
[Cr(NH3)6]3+

mixing

d1 d9

mixing

## Ground state mixing

E (T1g→A2g) - E (T1g→T2g) = ∆o