Effective hamiltonian of crystal field method for periodic systems containing transition metals

Abstract

Effective Hamiltonian of Crystal Field (EHCF) is a hybrid quantum chemical method originally developed for an accurate treatment of highly correlated d-shells in molecular complexes of transition metals. In the present work, we generalise the EHCF method to periodic systems containing transition metal atoms with isolated d-shells, either as a part of their crystal structure or as point defects. A general solution is achieved by expressing the effective resonance interactions of an isolated d-shell with the band structure of the crystal in terms of the Green's functions represented in the basis of local atomic orbitals. Such representation can be obtained for perfect crystals and for periodic systems containing atomic scale defects. Our test results for transition metal oxides (MnO, FeO, CoO, and NiO) and MgO periodic solid containing transition metal impurities demonstrate the ability of the EHCF method to accurately reproduce the spin multiplicity and spatial symmetry of the ground state. For the studied materials, these results are in a good agreement with experimentally observed d-d transitions in optical spectra. The proposed method is discussed in the context of modern solid state quantum chemistry and physics.