Origin of accidental degeneracy in ligand-field splittings of substituted octahedral complexes

Abstract

Accidental degeneracy seems to be the rule rather than an exception amongst thed orbital energies of substituted octahedral complexes of d¹ configuration. By using symmetry and physical arguments, in conjunction with first-order and second-order degenerate perturbation theory, it is shown that such accidental degeneracies arise in crystal-field theory due to the choice of an inflexible basis set of metal orbitals which neglects the polarisation of metal orbitals by the ligand charges.