The Theory of Electron Transfer Reactions:  What May Be Missing?

TitleThe Theory of Electron Transfer Reactions:  What May Be Missing?
Publication TypeJournal Article
Year of Publication2003
AuthorsSmall, DW, Matyushov, DV, Voth, GA
JournalJ Am Chem Soc
Volume125
Pagination7470-8
KeywordsChemical *Thermodynamics, Computer Simulation Electrons *Models
Abstract

Molecular dynamics simulations are presented for condensed-phase electron transfer (ET) systems where the electronic polarizability of both the solvent and the solute is incorporated. The solute polarizability is allowed to change with electronic transition. The results display notable deviation from the standard free energy parabolas of traditional ET theories. A new three-parameter ET model is applied, and the theory is shown to accurately model the free energy surfaces. This paper presents conclusive evidence that the traditional theory for the free energy barrier of ET reactions requires modification.

DOI10.1021/ja029595j