Interatomic exchange energy components

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)174-180
Number of pages7
JournalInternational Journal of Quantum Chemistry
Volume92
Issue number2 SPEC.
DOIs
Publication statusPublished - Mar 15 2003

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Electrostatics
energy transfer
chemical energy
electrostatics
orbitals
energy
approximation

Keywords

  • Bond order indices
  • Bonding orbitals
  • Energy partitioning
  • Exchange energy
  • Interatomic exchange

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Interatomic exchange energy components. / Mayer, I.; Hamza, A.

In: International Journal of Quantum Chemistry, Vol. 92, No. 2 SPEC., 15.03.2003, p. 174-180.

Research output: Contribution to journalArticle

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