Perturbative calculation of intermolecular interactions in orthogonalized or biorthogonal basis sets

P. R. Surján, C. Pérez Del Valle

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Two versions of a many-body perturbation theory for the computation of molecular interaction energies are investigated. The methods are based on the partitioning of the second-quantized form of the dimer Hamiltonian written either in the orthogonalized basis of the monomer MOs, or, alternatively, in the original non-orthogonal dimer basis set handling the overlap by the biorthogonal formalism. The zeroth-order Hamiltonian H0 is the sum of effective monomer Fockians and the zeroth-order wave functions are exact eigenfunctions of H0. Full antisymmetry is ensured by the second-quantized formalism. Basis set superposition error is accounted for by the counterpoise correction recipe. Results for He2, (H2)2 and (H2O)2 indicate the reliability of the biorthogonal technique.

Original languageEnglish
Pages (from-to)333-344
Number of pages12
JournalTheoretical Chemistry Accounts
Volume94
Issue number6
DOIs
Publication statusPublished - 1996

Keywords

  • Biorthogonal basis
  • Intermolecular interactions
  • Perturbation theory
  • Second quantization

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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