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Analysis of molecular orbital wave functions in terms of valence bond functions for molecular fragments. I. Theory
Author(s) -
Hiberty P. C.
Publication year - 1981
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.560190207
Subject(s) - valence bond theory , molecular orbital , delocalized electron , wave function , molecular orbital theory , modern valence bond theory , fragment molecular orbital , localized molecular orbitals , chemistry , molecular orbital diagram , atomic orbital , valence (chemistry) , computational chemistry , non bonding orbital , orbital hybridisation , molecule , generalized valence bond , linear combination of atomic orbitals , slater type orbital , molecular physics , atomic physics , physics , quantum mechanics , electron
A method of expansion of molecular orbital wave functions into valence bond ( VB ) functions is extended to molecular fragments. The wave function is projected onto a basis of mixed determinants, involving molecular orbitals as well as fragment atomic orbitals, and is further expressed as a linear combination of VB functions, characteristic of structural formulas of the fragment but whose remaining bonds are frozen. Structural weights for the fragment are deduced from this expression. Delocalized molecular orbitals are used as a startpoint, as they are after an ordinary SCF calculation. Wave functions of medium‐sized molecules may be analyzed with reasonable storage requirements in a computer.