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Extremal electron pairs
Author(s) -
Kutzelnigg Werner,
Vogtner Stefan
Publication year - 1996
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/(sici)1097-461x(1996)60:1<235::aid-qua25>3.0.co;2-c
Subject(s) - wave function , uncorrelated , limit (mathematics) , electron , electron pair , physics , spin (aerodynamics) , function (biology) , electronic correlation , quantum mechanics , open shell , chemistry , statistical physics , mathematics , mathematical analysis , thermodynamics , statistics , evolutionary biology , biology
Abstract Extremal pair functions for an n ‐electron wave function of a closed‐shell state are defined as linear combinations of spin‐orbital‐product pair functions that make some functionals (e.g., r 2 12 or r −1 12 ) extremal. They are related to the natural spin geminals in the uncorrelated limit and are useful both for an analysis of wave functions in view of an understanding of the chemical bond and for the treatment of electron correlation. Numerical examples are shown and discussed for He 2 as well as the 10‐electron systems Ne, HF, H 2 O, NH 3 , and CH 4 . © 1996 John Wiley & Sons, Inc.