Curvilinear-path based theory of the energy transfer limited rate of a two-dimensional solute in a dissipative bath Original Research Article

We present a new theory for predicting the energy-diffusion-limited rate constant for the thermally-activated barrier crossing of a two-dimensional solute in a dissipative solvent bath. By using a unique, reaction-path-based periodic trajectory to compute the average energy lost from the solute to the bath, our theory takes into account the time dependence of the intramolecular energy transfer. As a result, it describes the competition between inter- and intramolecular energy transfer mechanisms, and can describe the crossover of the rate constant from one-dimensional to two-dimensional (RRKM) rate behavior as the intramolecular coupling strength is increased.