Theoretica chimica acta

, Volume 83, Issue 5, pp 389–416

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


  • A. V. Soudackov
    • Karpov Institute of Physical Chemistry
  • A. L. Tchougreeff
    • Karpov Institute of Physical Chemistry
  • I. A. Misurkin
    • Karpov Institute of Physical Chemistry

DOI: 10.1007/BF01113064

Cite this article as:
Soudackov, A.V., Tchougreeff, A.L. & Misurkin, I.A. Theoret. Chim. Acta (1992) 83: 389. doi:10.1007/BF01113064


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 MF64− (M=Mn, Fe, Co, Ni) anions, Mn(FH)62+ cation, CoCl64− anion, and a tetrahedral CoCl42− anion. The values of the parameters are reasonable, thus confirming the validity of the proposed scheme.

Key words

Electronic structureTransition metal complexesd-d-excitation spectraEffective Hamiltonian
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© Springer-Verlag 1992