Communication: Transition-path velocity as an experimental measure of barrier crossing dynamics

Abstract

Experimental observation of transition paths - short events when the system of interest crosses the free energy barrier separating reactants from products - provides an opportunity to probe the dynamics of barrier crossing. Yet limitations in the experimental time resolution usually result in observing trajectories that are smoothed out, recross the transition state fewer times, and exhibit apparent velocities that are much lower than the instantaneous ones. Here we show that it is possible to define (and measure) an effective transition-path velocity which preserves exact information about barrier crossing dynamics in the following sense: the exact transition rate can be written in a form resembling that given by transition-state theory, with the mean thermal velocity replaced by the transition-path velocity. In addition, the transition-path velocity (i) ensures the exact local value of the unidirectional reactive flux at equilibrium and (ii) leads to the exact mean transition-path time required for the system to cross the barrier region separating reactants from products. We discuss the coordinate dependence of the transition path velocity and derive analytical expressions for it in the case of diffusive dynamics. These results can be used to discriminate among models of barrier crossing dynamics in single-molecule force spectroscopy studies.