skip to main content

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

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.
Authors:
; ; ; ;  [1]
  1. Department of Chemical Engineering, Imperial College London, South Kensington Campus, London SW72AZ (United Kingdom)
Publication Date:
OSTI Identifier:
22493698
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 144; Journal Issue: 4; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHEMISTRY; FLUCTUATIONS; FREE ENERGY; INTERFACES; LAYERS; LENNARD-JONES POTENTIAL; LIQUIDS; PATH INTEGRALS; SAMPLING; VAPORS