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Updated: Mar 26, 2026

Orientational Transition in a Liquid Crystal Triggered by the Thermodynamic Growth of Interfacial Wetting Sheets
Published on: May 15, 2017
Nonequilibrium study of the intrinsic free-energy profile across a liquid-vapour interface
Carlos Braga1, Jordan Muscatello1, Gabriel Lau1
1Department of Chemical Engineering, Imperial College London, South Kensington Campus, London SW72AZ, United Kingdom.
Abstract:
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.
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