Crystal-field splittings and optical spectra of transition-metal mixed-ligand complexes by effective hamiltonian method

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

Research output: Contribution to journalArticlepeer-review

Abstract

Many of the important properties of transition-metal complexes depend on the low-energy excitation spectrum formed by d-electrons of the central transition-metal atom. The spectra of this type are usually fit to the well-known crystal field theory or to the angular overlap model. The result of the fitting is a set of parameters which are considered as characteristics of the electronic structure of the complex such as strength of the ligand field or types and extent of metal-ligand bonding. We present here a short account of the effective Hamiltonian method recently developed to calculate the splitting of the d-levels by the ligands and the resulting d-d spectra of transition-metal complexes together with some results of its application to the mixed-ligand complexes with the general formula ML4Z2, where M = V, Co, Ni; L = H2O, NH3, Py; and Z = H2O, NCS-, Cl-. Particular attention is paid to the V(H2O)4Cl2 and Co(H2O)4Cl2 compounds. The former seems to have tetragonal structure, whereas for the latter, our method predicts a spatially degenerate ground state for the tetragonal arrangement of the ligands. That must lead to the Jahn-Teller distortion, which is actually observed.

Original languageEnglish (US)
Pages (from-to)663-671
Number of pages9
JournalInternational Journal of Quantum Chemistry
Volume57
Issue number4
DOIs
StatePublished - Feb 15 1996
Externally publishedYes

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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