Influence of Spin State and Cation Distribution on Stability and Electronic Properties of Ternary Transition-Metal Oxides

This work is a systematic ab initio study of the influence of spin state and cation distribution on the stability, dielectric constant, electronic band gap, and density of states of ternary transition-metal oxides. As an example, the chemical family of spinel ferrites MFe2O4, with M = Mg, Sc-Zn is chosen. Dielectric constant and band gap are calculated for various spin states and cation configurations via dielectric-dependent self-consistent hybrid functionals and compared to available experimental data. When choosing the most stable spin state and cation configuration, the calculated electronic properties are in reasonable agreement with measured values. The nature of the excitation is investigated through projected density of states. A pronounced dependence of band gap energy and dielectric constant on the spin state and cation configuration is observed, which is a possible explanation for the large variation of the experimental results, in particular, if several states are energetically close.