Additive eigenvectors as optimal reaction coordinates, conditioned trajectories, and time-reversible description of stochastic processes.

Abstract

A fundamental way to analyze complex multidimensional stochastic dynamics is to describe it as diffusion on a free energy landscape-free energy as a function of reaction coordinates (RCs). For such a description to be quantitatively accurate, the RC should be chosen in an optimal way. The committor function is a primary example of an optimal RC for the description of equilibrium reaction dynamics between two states. Here, additive eigenvectors (addevs) are considered as optimal RCs to address the limitations of the committor. An addev master equation for a Markov chain is derived. A stationary solution of the equation describes a sub-ensemble of trajectories conditioned on having the same optimal RC for the forward and time-reversed dynamics in the sub-ensemble. A collection of such sub-ensembles of trajectories, called stochastic eigenmodes, can be used to describe/approximate the stochastic dynamics. A non-stationary solution describes the evolution of the probability distribution. However, in contrast to the standard master equation, it provides a time-reversible description of stochastic dynamics. It can be integrated forward and backward in time. The developed framework is illustrated on two model systems-unidirectional random walk and diffusion.