title: The free energy of expansion and contraction: treatment of arbitrary systems using the Jarzynski equality.
abstract: Thermodynamic integration, free energy perturbation, and slow change techniques have long been utilised in the calculation of free energy differences between two states of a system that has undergone some transformation. With the introduction of the Jarzynski equality and the Crooks relation, new approaches are possible. This paper investigates an important phenomenon - systems undergoing a change in volume/density - and derives both the Jarzynski equality and Crooks relation of such systems using a statistical mechanical approach. These results apply to systems with arbitrary particle interactions and densities. The application of this approach to the expansion/compression of particles confined within a vessel with a piston and within a periodic system is considered.
authors.affiliation: Queensland Micro- and Nanotechnology Centre and School of Biomolecular and Physical Sciences, Griffith University, Brisbane, Queensland 4111, Australia.
authors.forename: Stuart J
authors.initials: SJ
authors.lastname: Davie
authors.forename: James C
authors.initials: JC
authors.lastname: Reid
authors.forename: Debra J
authors.initials: DJ
authors.lastname: Searles
mesh_terms: D000465:Algorithms; D003198:Computer Simulation; D019277:Entropy; D008956:Models, Chemical; D008962:Models, Theoretical; D013816:Thermodynamics