A nonempirical effective Hamiltonian technique for polymers: Application to polyacetylene and polydiacetylene

Jean-Luc Bredas*, R. R. Chance, R. Silbey, G. Nicolas, Ph Durand

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

269 Scopus citations

Abstract

The recently proposed ab initio effective Hamiltonian technique is extended to polymer calculations and applied to various conformations of polyacetylene (all-trans, cis-transoid, and trans-cisoid) and polydiacetylene (acetylenic and butatrienic backbones). Band structures, density of states (DOS), and XPS theoretical spectra are presented. Comparison of the band structures and DOS with those obtained by ab initio SCF (self-consistent-field) Hartree-Fock calculations of double zeta quality is excellent. The XPS theoretical spectrum for all-trans polyacetylene is in good agreement with experiment. In polyacetylene, it is found that the π bands are quite similar for all three backbone conformations, though the π bands differ significantly. For polydiacetylene, low ionization potentials are predicted-a few tenths of an eV larger than polyacetylene for the acetylenic backbone and a few tenths of an eV smaller than polyacetylene for the butatrienic backbone.

Original languageEnglish (US)
Pages (from-to)255-267
Number of pages13
JournalThe Journal of Chemical Physics
Volume75
Issue number1
DOIs
StatePublished - Jan 1 1981

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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