Nonequilibrium study of the intrinsic free-energy profile across a liquid-vapour interface

作者：Braga Carlos; Muscatello Jordan; Lau Gabriel; Mueller Erich A; Jackson George^*

来源：Journal of Chemical Physics, 2016, 144(4): 044703.

DOI：10.1063/1.4940137

We calculate an atomistically detailed free-energy profile across a heterogeneous system using a nonequilibrium approach. The path-integral formulation of Crooks fluctuation theorem is used in conjunction with the intrinsic sampling method to calculate the free-energy profile for the liquid-vapour interface of the Lennard-Jones fluid. Free-energy barriers are found corresponding to the atomic layering in the liquid phase as well as a barrier associated with the presence of an adsorbed layer as revealed by the intrinsic density profile. Our findings are in agreement with profiles calculated using Widom's potential distribution theorem applied to both the average and the intrinsic profiles as well as the literature values for the excess chemical potential.

• 出版日期2016-1-28