Applications of the MBPT in the localized representation

Ede Kapuy, Ferenc Bartha, F. Bogár, Zoltán Csépes, Cornelia Kozmutza

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

Diagrammatic formulation of the MBPT is applied when the occupied and the virtual canonical orbitals are separately localized by unitary transformations. In this localized representation, due to the off‐diagonal Fock matrix elements, the perturbation operator contains extra terms generating the so‐called localization corrections. These corrections enter the perturbation energy in third and higher orders. Their magnitude depends on the type of localization, but they represent only a small fraction of the canonical corrections. The calculation of the localization corrections, however, does not need a significant amount of extra computer time. It is shown that by introducing an “order of neighborhood” local and nonlocal effects of the electron correlation can be separated and the contribution of the nonlocal effects can be neglected to a good approximation. Ab initio calculations have been carried out for the normal saturated hydrocarbons: C2n+1H4n+4 and for the all‐trans conjugated polyenes C2n+2H2n+4. As to the ratio of the local and nonlocal corrections, it is shown that there is only a quantitative difference for these two kinds of systems (strongly or weakly localizable). Neglecting nonlocal effects, considerable amount of computer time can be saved.

Original languageEnglish
Pages (from-to)139-147
Number of pages9
JournalInternational Journal of Quantum Chemistry
Volume38
Issue number2
DOIs
Publication statusPublished - 1990

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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