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

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Summary

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 4−6 (M=Mn, Fe, Co, Ni) anions, Mn(FH) 2+6 cation, CoCl 4−6 anion, and a tetrahedral CoCl 2−4 anion. The values of the parameters are reasonable, thus confirming the validity of the proposed scheme.

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Authors and Affiliations

  1. Karpov Institute of Physical Chemistry, K-64, ul. Obuhka, 10, 103064, Moscow, Russia

    A. V. Soudackov, A. L. Tchougreeff & I. A. Misurkin

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  1. A. V. Soudackov
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  2. A. L. Tchougreeff
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  3. I. A. Misurkin
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Soudackov, A.V., Tchougreeff, A.L. & Misurkin, I.A. Electronic structure and optical spectra of transition metal complexes by the effective Hamiltonian method. Theoret. Chim. Acta 83, 389–416 (1992). https://doi.org/10.1007/BF01113064

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  • DOI: https://doi.org/10.1007/BF01113064

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