Electronic decoherence in condensed phases

The impact of electronic decoherence on electronic dynamics, and electron t ransfer (ET) reactions in particular, in condensed phase environments is di scussed. Analytical expressions are considered for a common model system in which ET occurs between relatively displaced harmonic surfaces. We identif y a relationship in the semi-classical Marcus limit between electronic deco herence and the Wigner distribution of nuclear configurations. Generalizati on to more complex surfaces is discussed. Additionally, we discuss electron ic decoherence for ET via so-called bridge sites in materials, for both dir ect (superexchange) mechanisms and sequential mechanisms of ET. Quantitativ e simulation studies of factors affecting characteristic decoherence times for ET in solution are also presented and discussed. (C) 2001 Elsevier Scie nce.