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What is the meaning of selection rule related to UV spectroscopy?
Yaranabil
The Selection Rules governing transitions between electronic energy levels of transition metal complexes are:
- ΔS = 0 The Spin Rule
- Δl = +/- 1 The Orbital Rule (Laporte)
The first rule says that allowed transitions must involve the promotion of electrons without a change in their spin.
The second rule says that if the molecule has a centre of symmetry, transitions within a given set of p or d orbitals (i.e. those which only involve a redistribution of electrons within a given subshell) are forbidden.
Relaxation of the Rules can occur through:
- a) Spin-Orbit coupling - this gives rise to weak spin forbidden bands
- b) Vibronic coupling - an octahedral complex may have allowed vibrations where the molecule is asymmetric.
Absorption of light at that moment is then possible.
- c) π-acceptor and π-donor ligands can mix with the d-orbitals so transitions are no longer purely d-d.
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