Zero‐field splitting of 6S(d5) ions in tetragonal and rhombic symmetry. II. Application of complete d‐electron calculations to the zero‐field splitting in Mn:MnF2 and Mn:ZnF2

Abstract

The results of a complete d‐electron calculation for configuration 3d⁵ of orthorhombic symmetry are applied to a study of zero‐field splitting in Mn²⁺:MnF₂ and Mn²⁺:ZnF₂. The parameters are determined from the optical spectra of the crystals by a least squares fit and adjusted by conditions governing the zero‐field splitting. The results for Mn²⁺:ZnF₂, D = −180.0 × 10⁻⁴ cm⁻¹, E = −42.2 × 10⁻⁴ cm⁻¹ are in excellent agreement with the experimental values D = (−186 ± 7.5) × 10⁻⁴ cm⁻¹, E = (−41 ± 12.5) × 10⁻⁴ cm⁻¹. The data for Mn²⁺:MnF₂ are used to estimate the unknown covalency contribution. All contributions fit into a regular and consistent pattern.