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The Selection Rules governing transitions between electronic energy levels of transition metal complexes are:

  1. ΔS = 0 The Spin Rule
  2. 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) Ï€-acceptor and Ï€-donor ligands can mix with the d-orbitals so transitions are no longer purely d-d.
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