Abstract
The ground-state electronic and magnetic properties of rhombohedral and have been investigated by ab initio all-electron periodic Hartree-Fock calculations. Both unrestricted open-shell and restricted closed-shell methods have been employed, with basis sets of atomic orbitals represented by contracted Gaussian-type functions. The degeneracy of d electrons is removed by the rhombohedral field, giving rise to orbital ordering between and levels. The self-consistent-field variational solutions are spin-polarized insulating states with single () and double () electron occupations for and , respectively. Conducting or semiconducting states, with different relative energies of and bands, have also been obtained by changing the c/a ratio of the hexagonal unit cell. The charge transfer into levels is discussed and compared to the and behavior.
DOI:https://doi.org/10.1103/PhysRevB.55.16122
©1997 American Physical Society