Using bijective maps to improve free-energy estimates

Abstract

We derive a fluctuation theorem for generalized work distributions, related to bijective mappings of the phase spaces of two physical systems, and use it to derive a two-sided constraint maximum likelihood estimator of their free-energy difference which uses samples from the equilibrium configurations of both systems. As an application, we evaluate the chemical potential of a dense Lennard-Jones fluid and study the construction and performance of suitable maps.