Free energies and optimal reaction coordinates via entropy production

Abstract

We show through theory and numerical experiments that a straightforward calculation of entropy production on short molecular dynamics trajectories allows estimating free-energy barriers and identifying optimal reaction coordinates of activated processes. To this aim, we perform an analysis based on stochastic energetics on a set of trajectories relaxing towards equilibrium from a same initial configuration, projected on different putative coordinates. After demonstrating the approach on simple benchmarks, we show that it is possible to estimate the free-energy barrier of a complex high-dimensional system (carbon nanoparticles in water) and to rank the quality of order parameters, in agreement with the committor probability. The results shed light on the entanglement between the second law, free-energy landscapes, reaction coordinates and kinetic rates.