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A variational biorthogonal valence bond method
Author(s) -
Malcolm Nathaniel O. J.,
McDouall Joseph J. W.
Publication year - 1994
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540151205
Subject(s) - modern valence bond theory , valence bond theory , generalized valence bond , biorthogonal system , valence (chemistry) , atomic orbital , orbital hybridisation , chemistry , ionic bonding , wave function , covalent bond , atomic physics , computational chemistry , quantum mechanics , molecular physics , physics , ion , computer science , wavelet transform , artificial intelligence , wavelet , electron
The details of a simple and efficient scheme for performing variational biorthogonal valence bond calculations are presented. A variational bound on the energy functional is obtained through the use of a complete configuration expansion in a well‐chosen subset of orbitals. The resultant wave functions are clearly dominated by the covalent (spin‐coupled) structures, with a negligible contribution from ionic structures. The orbitals obtained compare favorably with overlap enhanced atomic orbitals obtained by other valence bond approaches. The method is illustrated by calculations on water and dioxygen difluoride. © 1994 by John Wiley & Sons, Inc.