Efficient free energy profile reconstruction using adaptive stochastic perturbation protocols

TL;DR

This paper introduces an adaptive stochastic perturbation protocol that enhances the convergence of free energy estimates using Jarzynski's relation, especially under high dissipation conditions.

Contribution

It proposes a novel adaptive external work variation method to improve free energy profile reconstruction accuracy and convergence.

Findings

Enhanced convergence of Jarzynski estimator with the new protocol

Reduced dissipation effects in free energy calculations

Improved accuracy in potential of mean force reconstruction

Abstract

Application of Jarzynski nonequilibrium work relation to free energy calculation is limited by the very slow convergence of the estimate when dissipation is high. We present a novel perturbation protocol able to improve the convergence of Jarzynski estimator when it is applied in the reconstruction of the potential of mean force. The improvement is based on the application of the adaptive external work variation in addition to the one caused by thermal fluctuations.