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Interatomic exchange energy components
Author(s) -
Mayer I.,
Hamza A.
Publication year - 2003
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.10504
Subject(s) - diatomic molecule , delocalized electron , component (thermodynamics) , intermolecular force , coulomb , statistical physics , chemistry , analogy , limit (mathematics) , energy (signal processing) , exchange interaction , atomic orbital , physics , quantum mechanics , molecule , mathematics , mathematical analysis , linguistics , philosophy , ferromagnetism , electron
The diatomic energy components obtained in the framework of the recent chemical energy component analysis can be further decomposed into terms of different physical origins, reflecting electrostatic, exchange, overlap, etc., effects. The proper definition of the interatomic exchange energy component represented a nontrivial task, however. Here, we considered two possible definitions of that quantity. The first is introduced following the definition of the intermolecular exchange. This seemingly straightforward analogy has been found misleading—it leads to a quantity that vanishes in the limit of an NDO‐type integral approximation. The correct definition has been found by analyzing the exchange energy components connected with the delocalized bonding orbitals in a diatomics and generalizing the interatomic exchange energy contribution obtained in this simplest case by the analogy to the respective Coulomb energy component. This definition is adequate for all types of theories, has the correct asymptotic behavior, and exhibits the expected connections with the bond order indices. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003