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A unified treatment of valence and bond order from density operators
Author(s) -
Jug Karl
Publication year - 1984
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.540050608
Subject(s) - valence (chemistry) , atomic orbital , valence bond theory , chemistry , atomic physics , diatomic molecule , linear combination of atomic orbitals , generalized valence bond , modern valence bond theory , molecule , generalization , computational chemistry , slater type orbital , basis set , molecular orbital , quantum mechanics , density functional theory , physics , mathematics , electron , mathematical analysis
A generalization of the quantum chemical definition of valence of atoms in molecules is suggested. Valence is considered as expectation value of diatomic parts of density operators. It appears as a sum of contributions from occupied orbitals of all atomic pairs that contain the reference atom. This definition is applicable on self‐consistent‐field ( SCF ) and configuration interaction ( CI ) level in any atomic orbitals ( AO ) basis. Its usefulness is demonstrated in an application to special molecules. Photoelectron spectroscopy and reactivity is discussed in this context.