Electronic structure and orbital ordering in perovskite-type 3<i>d</i>transition-metal oxides studied by Hartree-Fock band-structure calculations

Abstract

We have studied transition-metal 3d-oxygen 2p lattice models, where full degeneracy of transition-metal 3d and oxygen 2p orbitals and on-site Coulomb and exchange interactions between 3d electrons are taken into account, by means of a spin- and orbital-unrestricted Hartree-Fock (HF) approximation. The electronic-structure parameters deduced from the cluster-model analyses of the photoemission spectra are used as input. We have applied this method to perovskite-type 3d transition-metal oxides, which exhibit various electrical and magnetic properties. It is shown that the HF results can explain the ground-state properties of insulating oxides. The relationship between spin- and orbital-ordered solutions and the Jahn-Teller-type and ${\mathrm{GdFeO}}_{3}$-type distortions in R${\mathrm{TiO}}_{3}$, R${\mathrm{VO}}_{3}$, R${\mathrm{MnO}}_{3}$, and R${\mathrm{NiO}}_{3}$ (R is a rare earth atom or Y) is extensively studied. Single-particle excitation spectra calculated using Koopmans' theorem give us an approximate but relevant picture on the electronic structure of the perovskite-type 3d transition-metal oxides. As a drawback, the HF calculations tend to overestimate the magnitude of the band gap compared with the experimental results and to predict some paramagnetic metals as antiferromagnetic insulators. \textcopyright{} 1996 The American Physical Society.