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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

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

Konfigurasi elektronik atom multi-elektron pasangan RS

Russell-Saunders (or LS) coupling

Untuk tiap atom multi-elektron L = total orbital angular momentum quantum number S = total spin angular momentum quantum number Spin multiplicity = 2S+1 ML = ml (-L,0,+L) MS = ms (S, S-1, ,0,-S)

Untuk tiap elektron 2p n = 2; l = 1 ml = -1, 0, +1 ms = 1/2

ML/MS menyatakan microstates L/S menyatakan states (kumpulan microstates) Group microstates dengan energi yang sama disebut terms

Menentukan microstates untuk p2

Spin multiplicity = 2S + 1

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

1S

2P

Mengklasifikasikan microstates p2

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 One remaining microstate ML is 0, L = 0 (an S term) and MS = 0 for ML = 0, 2S +1 = 1 1S

Spin multiplicity = # columns of microstates

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

Energy of terms (Hunds 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

before we did:
p2

ML & MS
Microstate Table

the largest ML L spin multiplicity = columns or 2S+1, S the largest MS

States (S, P, D) Spin multiplicity Terms 3P, 1D, 1S

Ground state term 3P

single e- (electronic state) multi-e- (atomic state)

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

Remember what were after ?

Theory to explain electronic excitations/transitions observed for metal complexes

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

Consequencies of selection rule

Type of transition Typical max/ dm3mol-1cm-1 <1 Example

Spin-forbidden d-d

High spin d5 [Mn(OH2)6]2+

Laporte forbidden, spin allowed d-d

Charge transfer (fully allowed)

1-10 10-1000
1000-50000

Centrosymmetric complexes (Oh) Non-centrosymmetric complexes (Td)

[MnO4]-

Breakdown of selection rules

Group theory analysis of term splitting

Free ion term for d2

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

Real complexes

Tanabe-Sugano diagrams

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

d2

Orgel diagrams
shows :
The information about the number of available terms of the same multiplicity as the multiplicity of the ground state for the case of weak ligand fields

allow us to assign absorption bands to some certain transitions in the order of their increased energy. We can also expect blue or red shifts in absorption spectra as the ligand field increases.

Energy T2

d4, d9 Oh d1, d6 Td

d1, d6 Oh d4, d9 Td

Eg

Energy d3, d8 O h 2 7 d , d Td T1(P) T1(F) T2

d2, d7 Oh d3, d8 Td

A2g T1g(P) T2g T1g(F)

E 0

T2g

A2 0

TS diagrams Other dn configurations

d3 d1 d9

d2

d8

Other configurations

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

symmetry labels