Ab initiocalculations of transition metal complexes
- 1 January 1974
- journal article
- research article
- Published by Taylor & Francis in Molecular Physics
- Vol. 27 (1), 215-223
- https://doi.org/10.1080/00268977400100181
Abstract
The He(I) photoelectron spectra of the isoelectronic series Fe(CO)2(NO)2, Co(CO)3NO and Ni(CO)4 are reported and interpreted by means of ab initio SCF-MO calculations. For the nitrosyl complexes it is found that ionization potentials calculated assuming Koopmans' theorem are seriously in error due to the considerably greater orbital relaxation accompanying ionization from metal than from NO valence orbitals. When such allowance is made for orbital relaxation by performing restricted Hartree-Fock (RHF) calculations on the ionic states, the experimental spectra are accurately reproduced and the observed similarity of the spectra of all three molecules is explained.Keywords
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