Molecular-Orbital Calculation of 10 Dq in Some Transition-Metal Fluorides
1967; American Institute of Physics; Volume: 47; Issue: 8 Linguagem: Inglês
10.1063/1.1712321
ISSN1520-9032
Autores Tópico(s)Inorganic Chemistry and Materials
ResumoUsing the ionic Hamiltonian model, the antibonding orbital separation 10Dq has been calculated for the tripositive metal hexafluorides CrF63− and FeF63−, and for the dipositive metal hexafluoride NiF64−. The calculated 10Dq is found to be about half of the experimental value in all three cases. Isotropic and anisotropic spin densities at the fluoride nuclei have also been calculated; the agreement between theory and experiment is poor in all cases. The results are discussed in the light of the approximations made in the ionic Hamiltonian model. A comparison of the present molecular-orbital method with the configuration-interaction approach of Hubbard et al. is given; it is shown that molecular-orbital theory is capable of taking into account all relaxation and polarization effects included in the configuration-interaction approach.
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