On the perturbation operator in ab initio theories of intermolecular interactions

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Abstract

Various forms of the perturbation operator describing interactions between two many-electron systems are discussed. These operators result from different partitionings of the total hamiltonian. It is shown that the requirement of the correct permutational symmetry, i.e. that H(0) and XXX possess the same symmetry as H, can only be satisfied if basis set expansion is not applied or if the underlying basis set is strictly complete. In matrix theories (second quantization) the usual form of the interaction operator can only be recovered if basis set superposition error (BSSE) terms are excluded from the hamiltonian.

Original languageEnglish
Pages (from-to)39-46
Number of pages8
JournalJournal of Molecular Structure: THEOCHEM
Volume226
Issue number1-2
DOIs
Publication statusPublished - Jan 15 1991

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Hamiltonians
Electrons
operators
perturbation
Mathematical operators
matrix theory
interactions
symmetry
requirements
expansion
electrons

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computational Theory and Mathematics
  • Atomic and Molecular Physics, and Optics

Cite this

On the perturbation operator in ab initio theories of intermolecular interactions. / Surján, P.

In: Journal of Molecular Structure: THEOCHEM, Vol. 226, No. 1-2, 15.01.1991, p. 39-46.

Research output: Contribution to journalArticle

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