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GVB–RP: A reliable MCSCF wave function for large systems

✍ Scribed by Francesco Faglioni; William A. Goddard III


Publisher
John Wiley and Sons
Year
1999
Tongue
English
Weight
614 KB
Volume
73
Category
Article
ISSN
0020-7608

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✦ Synopsis


We have developed a version of generalized valence bond GVB that overcomes the major weakness of the perfect pairing approximation without requiring a full transformation of the integrals at each step of the self-consistent orbital optimization.

Ž . The method, called generalized valence bond᎐restricted pairing GVB᎐RP , describes properly the dissociation of up to triple bonds and provides smooth potential energy surfaces for most chemical reactions. The wave functions obtained are a good starting point for more sophisticated computational techniques. The applicability of the method is illustrated with a few simple examples including multiple-bond dissociations, transition states for symmetry allowed, symmetry forbidden, and radical reactions, as well as reactions at a transition-metal center. The cost of the method compares well with other self-consistent correlated techniques.