TY - JOUR
T1 - Crystal-field splittings and optical spectra of transition-metal mixed-ligand complexes by effective hamiltonian method
AU - Soudackov, A. V.
AU - Tchougreeff, A. L.
AU - Misurkin, I. A.
N1 - Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 1996/2/15
Y1 - 1996/2/15
N2 - 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.
AB - 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.
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U2 - 10.1002/(SICI)1097-461X(1996)57:4<663::AID-QUA13>3.0.CO;2-1
DO - 10.1002/(SICI)1097-461X(1996)57:4<663::AID-QUA13>3.0.CO;2-1
M3 - Article
AN - SCOPUS:0000291171
SN - 0020-7608
VL - 57
SP - 663
EP - 671
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
IS - 4
ER -