In the present work the semiempirical effective crystal field (ECF) method previously designed for electronic structure calculations of transition metal complexes and utilizing non-Hartree-Fock trial wave function and parameterized for complexes of doubly charged Cr 2ϩ , V 2ϩ , Mn 2ϩ , Fe 2ϩ , Co 2ϩ , and Ni 2ϩ cations is extended to complexes of triply charged cations of 3d-elements. With the parameters adjusted the ECF method is applied to calculations of ground states and low-energy spectra of the d-shells of fluoro-, chloro-, aqua-, amino-, and cyano-complexes of the triply charged cations. Obtained total spin and symmetry of the ground states match the experimentally observed ones. Satisfactory agreement between the calculated and experimental d-shell electronic transition energies is achieved as well.

ABSTRACT:In the present work the semiempirical effective crystal field (ECF) method previously designed for electronic structure calculations of transition metal complexes and utilizing non-Hartree-Fock trial wave function and parameterized for complexes of doubly charged Cr 2ϩ , V 2ϩ , Mn 2ϩ , Fe 2ϩ , Co 2ϩ , and Ni 2ϩ cations is extended to complexes of triply charged cations of 3d-elements. With the parameters adjusted the ECF method is applied to calculations of ground states and low-energy spectra of the d-shells of fluoro-, chloro-, aqua-, amino-, and cyano-complexes of the triply charged cations. Obtained total spin and symmetry of the ground states match the experimentally observed ones. Satisfactory agreement between the calculated and experimental d-shell electronic transition energies is achieved as well.