Local distortion and zero-field splittings of 3d⁵ ions in oxide crystals

A lattice relaxation model is employed to calculate the distorted ligand positions of Mn²⁺ and Fe³⁺ doped in cubic sites of some alkaline-earth metal oxides and the non-cubic sites of Fe³⁺:MgO as well. A superposition model analysis is then carried out for the spin parameters of the ⁶S_5/2 ground-state zero-field splittings of both 3d⁵ ions. A consistent set of intrinsic parameters is obtained which gives good predictions for the spin parameters of Fe³⁺ in non-cubic sites of MgO and Mn²⁺ in the C_3i site of some garnets. Copyright © 1988 IOP Publishing Ltd.