The impact of symmetric modes on intramolecular electron transfer: A semi-classical approach

Veaceslav Coropceanu, Sergei I. Boldyrev, Chad Risko, Jean Luc Brédas

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

We have generalized the Hush equations developed for the analysis of intervalence charge-transfer bands by including into the model the interaction with symmetric vibrations. Our results indicate that in symmetric class-II systems the maximum of the intervalence charge-transfer band is equal to the reorganization energy λ related to the antisymmetric vibrations as is the case in the conventional Hush model. In contrast, the corresponding transition dipole moment and the activation barrier for thermal electron transfer, in addition to their dependence on λ, also depend on the reorganization energy L related to symmetric vibrational modes. We show that the interaction with symmetric vibrational modes reduces the activation barrier and that the thermal electron-transfer rates derived on the basis of a Hush-type analysis of the optical data are generally underestimated.

Original languageEnglish
Pages (from-to)107-114
Number of pages8
JournalChemical Physics
Volume326
Issue number1
DOIs
StatePublished - Jul 11 2006

Bibliographical note

Funding Information:
The work at Georgia Tech is partly supported by the National Science Foundation, through the STC Program for Materials and Devices for Information Technology – DMR-0120967 and through grant CHE-0343321, and by the Office of Naval Research. We thank one of the reviewers for valuable suggestions.

Keywords

  • Electron transfer
  • Mixed-valence
  • Vibronic coupling

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry

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