Journal of Chemical Physics, Vol.105, No.20, 9093-9103, 1996
Variational Transition-State Theory for Electron-Transfer Reactions in Solution
Variational transition state theory is used to compute the rate of nonadiabatic electron transfer for a model of two sets of shifted harmonic oscillators. The calculations provide new insight on the suitability of the energy gap as a reaction coordinate. The relationship to the standard generalized Langevin equation model of electron transfer is established, and provides a framework for the application of variational transition state theory in a realistic simulation of electron transfer in a microscopic (nonlinear) bath.
Keywords:ACTIVATED RATE-PROCESSES;INITIO MOLECULAR-DYNAMICS;FREE-ENERGY FUNCTIONS;CHARGE-TRANSFER;POLAR-SOLVENTS;NONADIABATIC TRANSITIONS;COMPUTER-SIMULATION;DISSIPATIVE SYSTEMS;CONDENSED PHASES;RATE CONSTANTS