Investigation of the local structure and the effects of the orbit reduction factor on the EPR g-factors for octahedral (CrO6) cluster in TiO2:Cr and MgO:Cr systems

A theoretical method for studying the inter-relation between electronic and molecular structure has been proposed based on the complete energy matrices for a d³ configuration ion in a tetragonal ligand-field. By means of this method, the local structure for Cr³⁺ ion doped in oxides TiO₂ (anatase) and MgO has been determined. The calculated results indicate that the local structure of the (CrO₆)⁹⁻ cluster in TiO₂:Cr³⁺ and MgO:Cr³⁺ systems exists as a compressed distortion relative to the regular octahedron. Meanwhile, the dependence of the EPR zero-field splitting parameter D on the local structure parameter ΔR (ΔR=R₁−R₂) has been revealed. In addition, the relation between the EPR g-factors (g,g,Δg) and the orbit reduction factor k has been discussed for the two systems, suggesting that the orbit reduction factor k is very important to understand the EPR g-factors.