Theoretica chimica acta

, Volume 83, Issue 5, pp 389-416

First online:

Electronic structure and optical spectra of transition metal complexes by the effective Hamiltonian method

  • A. V. SoudackovAffiliated withKarpov Institute of Physical Chemistry
  • , A. L. TchougreeffAffiliated withKarpov Institute of Physical Chemistry
  • , I. A. MisurkinAffiliated withKarpov Institute of Physical Chemistry

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A semiempirical effective Hamiltonian treatment is proposed for transition metal complexes, taking into accountd-electron correlations, weak covalency of the metal-ligand bonds and the electronic structure of the ligand sphere. The technique uses the variation wave function which differs from the usual Hartree-Fock antisymmetrized product of molecular orbitals extended over the whole complex. The scheme is implemented and parameters describing the metal-ligand interactions are adjusted to reproduced-d-excitation spectra of a number of octahedral MF 6 4− (M=Mn, Fe, Co, Ni) anions, Mn(FH) 6 2+ cation, CoCl 6 4− anion, and a tetrahedral CoCl 4 2− anion. The values of the parameters are reasonable, thus confirming the validity of the proposed scheme.

Key words

Electronic structure Transition metal complexes d-d-excitation spectra Effective Hamiltonian