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Non-exponentiality in electron transfer kinetics: Static versus dynamic disorder models
Authors:Biman Bagchi
Institution:(1) Solid State and Structural Chemistry Unit, Indian Institute of Science, 560 012 Bangalore, India;(2) Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore
Abstract:Non-exponential electron transfer kinetics in complex systems are often analyzed in terms of a quenched, static disorder model. In this work we present an alternative analysis in terms of a simple dynamic disorder model where the solvent is characterized by highly non-exponential dynamics. We consider both low and high barrier reactions. For the former, the main result is a simple analytical expression for the survival probability of the reactant. In this case, electron transfer, in the long time, is controlled by the solvent polarization relaxation—in agreement with the analyses of Rips and Jortner and of Nadler and Marcus. The short time dynamics is also non-exponential, but for different reasons. The high barrier reactions, on the other hand, show an interesting dynamic dependence on the electronic coupling element,V el.
Keywords:Non-exponential dynamics  adiabatic surface  solvent reorganization energy
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