Rate expressions for excitation transfer. III. An ab initio study of electronic factors in excitation transfer and exciton resonance interactions

Gregory D. Scholes, Richard D. Harcourt, Kenneth P. Ghiggino

Research output: Contribution to journalArticle

118 Scopus citations

Abstract

A detailed theory for electronic aspects of electronic excitation (energy) transfer (EET) for sandwich dimers was derived in paper II of this series [J. Chem. Phys. 101, 10 521 (1994)]. In II, the electronic transfer matrix element for EET was evaluated, then simplified to various levels of approximation. The results of ab initio molecular orbital calculations on an ethene sandwich dimer are reported here in order to test and quantify the theory of II. The calculations were undertaken using a STO-6G basis set and localized molecular orbitals, with separations of 4, 5, and 6 A° between the molecules. It is demonstrated that the important electronic factors contributing to EET are the Coulombic interaction (for direct singlet-singlet transfer) and, for both singlet-singlet and triplet-triplet EET, orbital overlap-dependent interactions. The dominant orbital overlap-dependent terms arise from through-configuration interaction, which involves successive one-electron transfers mediated via bridging ionic configurations, first presented in II. The results confirm that the Dexter-type exchange interaction is small in comparison.

Original languageEnglish (US)
Pages (from-to)9574-9581
Number of pages8
JournalThe Journal of chemical physics
Volume102
Issue number24
DOIs
StatePublished - Jan 1 1995
Externally publishedYes

All Science Journal Classification (ASJC) codes

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

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