Nonequilibrium study of the intrinsic free-energy profile across a liquid-vapour interface
- Department of Chemical Engineering, Imperial College London, South Kensington Campus, London SW72AZ (United Kingdom)
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.
- OSTI ID:
- 22493698
- Journal Information:
- Journal of Chemical Physics, Vol. 144, Issue 4; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
Unbiased free energy estimates in fast nonequilibrium transformations using Gaussian mixtures
Free energy reconstruction from steered dynamics without post-processing