Molecular dipole static polarisabilities and hyperpolarisabilities of conjugated oligomer chains calculated with the local π-electron coupled cluster theory

Vladimir V. Ivanov, Anton B. Zakharov, Ludwik Adamowicz

Research output: Contribution to journalArticle

6 Scopus citations

Abstract

A new semi-empirical π-electron local coupled cluster theory has been developed to calculate static dipole polarisabilities and hyperpolarisabilities of extended π-conjugated systems. The key idea of the approach is the use of the ethylene molecular orbitals as the orbital basis set for π-conjugated compounds (the method is termed the Covalent Unbonded Molecules of Ethylene method, cue). Test calculations of some small model organic conjugated compounds demonstrate high accuracy of the version of the cue local coupled cluster theory developed in this work in comparison with the π-electron full configuration interaction (FCI) method. Calculations of different conjugated carbon-based oligomer chains (polyenes, polyynes, polyacenes, polybenzocyclobutadiene, etc.) demonstrate fast convergence (per π-electron) of the polarisability and hyperpolarisability values in the calculations when more classes of orbital excitations are included in the coupled cluster single and double (CCSD) excitation operator. The results show qualitatively correct dependence on the system size.

Original languageEnglish (US)
Pages (from-to)3779-3792
Number of pages14
JournalMolecular Physics
Volume111
Issue number24
DOIs
StatePublished - Dec 1 2013

ASJC Scopus subject areas

  • Biophysics
  • Molecular Biology
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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