Dynamic Nature of the Intramolecular Electronic Coupling Mediated by a Solvent Molecule: A Computational Study

Alessandro Troisi, Mark A. Ratner, Matthew B. Zimmt

Research output: Contribution to journalArticlepeer-review

56 Citations (Scopus)

Abstract

We present a combined Molecular Dynamics/Quantum Chemical study of the solvent-mediated electronic coupling between an electron donor and acceptor in a C-clamp molecule. We characterize the coupling fluctuations due to the solvent motion for different solvents (acetonitrile, benzene, 1,3-diisopropylbenzene) for the charge separation and the charge recombination processes. The time scale for solvent-induced coupling fluctuation is ∼0.1 ps. The effect of these fluctuations on the observed rate is discussed using a recently developed theoretical model. We show that, while the microscopic charge transfer process is very complicated and its computational modeling very subtle, the macroscopic phenomenology can be captured by the standard models. Analyzing the contribution to the coupling given by different solvent orbitals, we find that many solvent orbitals mediate the electron transfer and that paths through different solvent orbitals can interfere constructively or destructively. A relatively small subset of substrate-solvent configurations dominate contributions to solvent-mediated coupling. This subset of configurations is related to the electronic structure of the C-clamp molecule.

Original languageEnglish
Pages (from-to)2215-2224
Number of pages10
JournalJournal of the American Chemical Society
Volume126
Issue number7
DOIs
Publication statusPublished - Feb 25 2004

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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