Electronic factors in the non-radiative relaxation of metal ions

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Abstract
The role of symmetry in the non-radiative relaxation of Cr3+ complex ions is considered by evaluating the relative rates of the 4 T 1g → 4 A 2g non-radiative relaxation in the cubic Cr(NH3)3+ 6 ion. By using a linear ligator approximation for the dynamics of the complex ion and a crystal field representation of the perturbation of the metal d-orbitals by the motion of the ligand ‘lone pair’ orbital and the hydrogen atoms, it is shown that the T 1g ligand rocking motion is rather ineffective in relaxing the 4 T 2g state to the 4 A 2g ground state. The importance of this in accounting for the luminescence of d 3 ions is considered.

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