A generalized valence bond representation of complete-active-space self-consistent-field (CASSCF) wave functions

A novel generalized valence bond wave function expressed in terms of local nonorthogonal orbitals is shown to attain nearly all of the correlation energy of a corresponding complete-active-space self-consistent-field (CASSCF) wave function. This new wave function allows for the local orbitals to var...

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Bibliographic Details
Published in:The Journal of chemical physics 1993-05, Vol.98 (10), p.7958-7968
Main Authors: MURPHY, R. B, MESSMER, R. P
Format: Article
Language:English
Subjects:
Atomic and molecular physics
Electron correlation calculations for atoms and molecules
Electronic structure of atoms, molecules and their ions: theory
Exact sciences and technology
Physics
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Summary:A novel generalized valence bond wave function expressed in terms of local nonorthogonal orbitals is shown to attain nearly all of the correlation energy of a corresponding complete-active-space self-consistent-field (CASSCF) wave function. This new wave function allows for the local orbitals to variationally respond to different spin couplings. The result is a very compact description of correlation effects contained in complex CASSCF expansions. The CASSCF expansion is also shown to contain a description of resonance among nonorthogonal valence bond structures.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.464550