Effective crystal field for trivalent first transition row ions

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.

DommiMOE: An implementation of ligand field molecular mechanics in the molecular operating environment

“…A general treatment would require expressing the stabilization energy in terms of the many-electron multiplet states as done in the ECF method. 27,36 This would be a complex undertaking with the AOM so instead, we have chosen to retain the simplicity of the orbital model and include an additional energy term, e pair , again expressed as in eq. (4), which allows the user to generate empirical parameter sets to capture the effects of interelectronic repulsion, and thus correctly describe the different spin state energies of metal complexes, without having to worry about full multiplets.…”