The generalized valence bond description of O2

A b initio calculations using the generalized valence bond (GVB) method have been carried out for the lowest triplet and singlet states of O2 at internuclear distances (R) between 2a0 and 6a0. In contrast to other orbital descriptions, GVB leads correctly to ground state oxygen atoms as the bond len...

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Bibliographic Details
Published in:The Journal of chemical physics 1975-01, Vol.63 (11), p.4632-4639
Main Authors: Moss, B. J., Bobrowicz, F. W., Goddard, W. A.
Format: Article
Language:English
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Summary:A b initio calculations using the generalized valence bond (GVB) method have been carried out for the lowest triplet and singlet states of O2 at internuclear distances (R) between 2a0 and 6a0. In contrast to other orbital descriptions, GVB leads correctly to ground state oxygen atoms as the bond length is increased to infinity. This proper behavior requires optimization of the spatial orbitals themselves and of the permutational coupling between them as well. Analysis of the results as a function of R is straightforward. Constructing a simple configuration interaction (CI) wavefunction using the GVB orbitals leads to excellent potential curves, accounting for 94% of the bond dissociation energy. The calculated adiabatic separation of the singlet and triplet states is 1.09 eV, which is 0.11 eV above the experimental Te.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.431248