Use of modern electron transfer theories to determine electronic coupling matrix elements in intramolecular systems

Journal Article (Journal Article)

The dependence of the donor/acceptor electronic coupling on the topology of donor-bridge-acceptor (DBA) molecules is probed experimentally and theoretically. The temperature dependence of photoinduced electron-transfer rate constants is analyzed with a semiclassical electron-transfer model to extract the donor/acceptor electronic coupling matrix elements |V| and the low-frequency reorganization energy at 295 K, λ0(295 K), for four rigid DBA molecules. The sensitivity of the electronic coupling |V| to the models and parameters used to fit the data are extensively investigated. The treatment of the low-frequency reorganization energy's temperature dependence has a significant impact on the analysis. The identity of the principal coupling pathways is determined for molecular linkages that propagate symmetry allowed donor/acceptor interactions and molecular linkages that propagate symmetry forbidden donor/acceptor interactions. For the symmetry forbidden case, these analyses demonstrate that solvent molecules provide the dominant coupling pathway in the nine-bond bridge, C-shaped molecule 2 but do not significantly influence |V| across the seven-bond, linear bridge in 1.

Full Text

Duke Authors

Cited Authors

  • Kumar, K; Kurnikov, IV; Beratan, DN; Waldeck, DH; Zimmt, MB

Published Date

  • July 9, 1998

Published In

Volume / Issue

  • 102 / 28

Start / End Page

  • 5529 - 5541

International Standard Serial Number (ISSN)

  • 1089-5639

Digital Object Identifier (DOI)

  • 10.1021/jp980113t

Citation Source

  • Scopus