Band gap, Jahn‐Teller deformation, octahedra rotation in transition metal perovskites LaTiO3$$ {}_3 $$

Abstract

AbstractThe LaTiO perovskite (where Ti is in a d1 state) is investigated by using an all electron Gaussian basis and many functionals, ranging from pure GGA (PBE), to hybrids (full range, B3LYP and PBE0, and range separated, HSE06) to Hartree Fock. Recently, Varignon et al. (Phys. Rev. Res 1, 033131, 2019), showed that, when GGA+U or HSE06 are used, a metallic solution and fractional occupancy of the t subshell are obtained. Here, it is shown that when a full range hybrid functional is used, an integer occupancy is obtained, as suggested by the Jahn‐Teller theorem. When the exact exchange percentage varies from 0 to 100, the system is insulating when it exceeds 20. By reducing progressively the symmetry from cubic down to orthorhombic, the relative importance of the Jahn‐Teller deformation and of the rotation of the octahedra is explored.