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The pairwise correlated generalized valence bond model of electronic structure. II. A simple physical model for electron correlation
Author(s) -
Petersson G. A.
Publication year - 1977
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.560110510
Subject(s) - generalized valence bond , wave function , atomic orbital , modern valence bond theory , valence bond theory , pairwise comparison , chemistry , valence (chemistry) , excited state , electronic correlation , chemical bond , invariant (physics) , electron , valence electron , atomic physics , molecular physics , physics , quantum mechanics , mathematics , statistics
When electron pair correlations are incorporated into generalized valence bond wave functions, the necessary and sufficient wave functions for the quantitative description of chemical reactions are achieved. The resulting electron pair correlation functions are shown to be invariant; hence the generalized valence bond orbitals contain all the information in the correlated wave functions. In the case of pair correlation energies, this information is expressed through a simple function of the orbital overlaps. The resulting overlap approximation is applied to ground states, excited states, and transition states for chemical reactions. In all cases the exact energy is reproduced to within 0.5 kcal/mol (0.001 hartree). The pairwise correlated generalized valence bond method provides an opportunity to accurately predict reaction pathways for system of chemical interest.