Deterministic Derivation of NonEquilibrium Free Energy Theorems for Natural Isothermal Isobaric Systems

TL;DR

This paper presents a deterministic derivation of nonequilibrium free energy theorems for isothermal isobaric systems, extending the Crooks and Jarzynski relations to such conditions and demonstrating their application through molecular dynamics simulations.

Contribution

It provides the first deterministic derivation of Crooks and Jarzynski relations for isothermal isobaric systems using a natural barostatting approach.

Findings

Validated relations with molecular dynamics simulations of polymer stretching

Extended free energy theorems to isothermal isobaric conditions

Demonstrated practical application of derived relations

Abstract

The nonequilibrium free energy theorems show how distributions of work along nonequilibrium paths are related to free energy differences between the equilibrium states at the end points of these paths. In this paper we develop a natural way of barostatting a system and give the first deterministic derivation of the Crooks and Jarzynski relations for these isothermal isobaric systems. We illustrate these relations by applying them to molecular dynamics simulations of a model polymer undergoing stretching.