Efficient schemes to compute diffusive barrier crossing rates

Abstract

The formulation of the classical barrier-crossing problem is reviewed in the context of numerical simulations, with the focus on barrier crossing problems where the reaction coordinate depends in a non-trivial way on the Cartesian coordinates of many particles. Often it is convenient to measure the barrier height using constrained dynamics. Such a calculation requires a knowledge of the Jacobian for the coordinate transformation between Cartesian and generalized ('reaction`) coordinates, and it is shown that the calculation of this Jacobian can be simplified. The conventional expression for the crossing rate is found to become computationally inefficient when the barrier crossing is diffusive. An alternative formulation of the barrier-crossing rate is given that leads to much better statistical accuracy in the computed crossing rates.