Transition path theory from biased simulations

Abstract

Transition Path Theory (TPT) provides a rigorous framework to investigate the dynamics of rare thermally activated transitions. In this theory, a central role is played by the forward committor function q⁺(x), which provides the ideal reaction coordinate. Furthermore, the reactive dynamics and kinetics are fully characterized in terms of two time-independent scalar and vector distributions. In this work, we develop a scheme which enables all these ingredients of TPT to be efficiently computed using the short non-equilibrium trajectories generated by means of a specific combination of enhanced path sampling techniques. In particular, first we further extend the recently introduced self-consistent path sampling algorithm in order to compute the committor q⁺(x). Next, we show how this result can be exploited in order to define efficient algorithms which enable us to directly sample the transition path ensemble.