The theory of electron transfer reactions: what may be missing?
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.
Small
David W
DW
Department of Chemistry and Henry Eyring Center for Theoretical Chemistry, 315 South 1400 East Rm 2020, University of Utah, Salt Lake City, Utah 84112-0850, USA.
Matyushov
Dmitry V
DV
Voth
Gregory A
GA
D003198:Computer Simulation; D004583:Electrons; D008956:Models, Chemical; D013816:Thermodynamics