Electron transfer in multiply bridged donor-acceptor molecules: Dephasing and quantum coherence

Randall H. Goldsmith, Michael R. Wasielewski*, Mark A. Ratner

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

55 Scopus citations


We present a simple theoretical treatment of nonadiabatic electron transfer in multiply bridged donor-bridge-acceptor molecules using the density matrix formalism. Destructive interference can result from different signed couplings between bridge sites, with the simplest system being a four-site Joachim-type molecular interferometer. Previous work has shown that deposition of energy on the bridge sites erases the interference and recovers transport. We show that pure local dephasing, a completely elastic process, is also capable of eliminating destructive interference and regaining transport. Destructive interference as a result of system connectivity can explain the familiar ortho-meta-para reactivity of benzene bridges. We also show that pure dephasing can yield a coalescence of ortho, meta, and para effective coupling strengths and suggest a system to observe this effect experimentally.

Original languageEnglish (US)
Pages (from-to)20258-20262
Number of pages5
JournalJournal of Physical Chemistry B
Issue number41
StatePublished - Oct 19 2006

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry


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