A Direct Simulation of Adiabatic Charge Transfer Through Bridged Organic Molecules

Abstract

Abstract We approach the dynamics of adiabatic charge transfer through bridged triarylamine cations by a direct molecular dynamics simulation involving classical and quantum mechanical degrees of freedom. Within a simple yet chemically specific model, the quantum mechanical subsystem is described by a tight-binding Hamiltonian, which is coupled to a classical force field. From a population analysis of the quantum part, the charge transfer rate can be readily extracted, including the influence of memory effects. The direct computation of the associated thermodynamic potential establishes a close link to analytical rate concepts. The theoretical data are compared to experiments, and the limits and possible extensions of our approach are discussed.