Rate expressions for excitation transfer. II. Electronic considerations of direct and through-configuration exciton resonance interactions

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

Research output: Contribution to journalArticle

180 Scopus citations

Abstract

The electronic interactions which promote singlet-singlet and triplet-triplet electronic excitation (energy) transfer (EET) are investigated in detail. Donor and acceptor locally excited configurations, ψ(A*B) and ψ4(AB*), respectively, are each allowed to mix with bridging ionic configurations, ψ2(A+B-) and ψ3(A-B+) to form the new donor and acceptor wave functions ΨR= ψ1+λψ2+μψ3 and ΨP4+μψ2+λψ 3. Use of the latter wave functions leads to the establishment of the matrix element TRP=〈ΨR|H-E1P〉≈=T14-(T12T24+T 13T34)/A, with Tij=〈ψi|H- E1j〉 and A = E2 - E1, as the exciton resonance interaction term for EET. Introduction of the Mulliken approximation shows that the "direct" exciton resonance interaction term (T14) contributes primarily a Coulombic interaction, for singlet-singlet EET, while the "through-configuration" exciton resonance interaction term [-(T12T24+T13T 34)/A] replaces the Dexter exchange integral (which is a component of H14) as the primary source of short-range orbital overlap-dependent EET. The origins of "Dexter-type" energy transfer are thus shown to be quite different from that originally outlined.

Original languageEnglish (US)
Pages (from-to)10521-10525
Number of pages5
JournalThe Journal of chemical physics
Volume101
Issue number12
DOIs
StatePublished - Jan 1 1994
Externally publishedYes

All Science Journal Classification (ASJC) codes

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

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