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Open‐shell valence configuration‐interaction studies of diatomic and polyatomic molecules
Author(s) -
Harris F. E.,
Michels H. H.
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560010639
Subject(s) - open shell , atomic physics , atomic orbital , diatomic molecule , valence (chemistry) , chemistry , slater type orbital , valence electron , molecular orbital , basis set , molecular orbital theory , electron configuration , molecular physics , electron , computational chemistry , molecule , physics , ion , quantum mechanics , density functional theory , organic chemistry
Systematic methods applicable to the study of open‐shell molecular configurations are described and applied to F 2 , HF, and BeH 2 . Complete valence‐shell spin‐projected calculations are carried out using Slater‐type and approximate Hartree‐Fock atomic orbitals as bases. Slater‐type orbitals yield good dissociation energies and equilibrium internuclear distances for F 2 and BeH 2 but have larger absolute errors than the Hartree‐Fock orbitals. The latter show systematic deviations which are discussed in detail. Subsidiary calculations indicate the small importance in F 2 and HF of configurations involving transfer of electrons from the fluorine K shell or from ∞ orbitals. The described methods use computation times far shorter than some alternative procedures of comparable or lesser accuracy.