Specific solvation effects on electron transfer

Kurt V. Mikkelsen, Mark A Ratner

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

This article focuses on the effects of specific solvation on electron transfer (ET) reactions and illustrates how differing configurations of solvent molecules can change the ET rate. The evolution of the ET system is given by a recently developed dynamical model for ET [1]. The dynamical model allows for evolution of the ET system dynamically coupled to the outer solvent and the intramolecular degrees of freedom. The evolution of the ET system is followed in direct time using time‐dependent statistical density operators. The initial state of the ET system is selected by a variational scheme, thereby determining an appropriate time‐dependent statistical density operator for the initial state. The electronic subsystem is treated by a full ab‐initio electronic Hamiltonian and allows for a detailed description of the electronic structure. The ET system consists of a donor, an acceptor, and a selection of solvent/bridge molecules; this encounter is surrounded by a dielectric medium [1, 2]. The actual calculations concern an ET system consisting of benzene anion radical as donor, benzene as acceptor, and three water molecules in the first solvation shell. These calculations show how important specific solvation of the donor‐acceptor complex is for the ET process. The ET probability can be increased or decreased depending on the configuration of the water molecules.

Original languageEnglish
Pages (from-to)707-720
Number of pages14
JournalInternational Journal of Quantum Chemistry
Volume34
Issue number22 S
DOIs
Publication statusPublished - 1988

Fingerprint

Solvation
solvation
electron transfer
Electrons
Molecules
Benzene
molecules
benzene
Hamiltonians
operators
Water
configurations
electronics
encounters
water
Electronic structure
Anions
degrees of freedom
electronic structure
anions

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

Specific solvation effects on electron transfer. / Mikkelsen, Kurt V.; Ratner, Mark A.

In: International Journal of Quantum Chemistry, Vol. 34, No. 22 S, 1988, p. 707-720.

Research output: Contribution to journalArticle

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