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Surface reconstruction amendment to the intrinsic sampling method

Surface reconstruction amendment to the intrinsic sampling method
Surface reconstruction amendment to the intrinsic sampling method
The intrinsic sampling method (ISM) is a powerful tool that allows the exploration of interfacial properties from molecular simulations by fitting a function that represents the local boundary between two phases. However, owing to the non-physical nature of an “intrinsic” surface, there remains an ambiguity surrounding the comparison of theoretical properties with the physical world. It is therefore important that the ISM remains internally consistent when reproducing simulated properties which match experiments, such as the surface tension or interfacial density distribution. We show that the current ISM procedure causes an over-fitting of the surface to molecules in the interface region, leading to a biased distribution of curvature at these molecular coordinates. We assert that this biased distribution is a cause of the disparity between predicted interfacial densities upon convolution to a laboratory frame, an artefact which has been known to exist since the development of the ISM. We present an improvement to the fitting procedure of the ISM in an attempt to alleviate the ambiguity surrounding the true nature of an intrinsic surface. Our “surface reconstruction” method is able to amend the shape of the interface so as to reproduce the global curvature distribution at all sampled molecular coordinates. We present the effects that this method has on the ISM predicted structure of a simulated Lennard-Jones fluid air-liquid interface. Additionally, we report an unexpected relationship between surface thermodynamic predictions of our reconstructed ISM surfaces and those of extended capillary wave theory, which is of current interest.
0021-9606
Longford, Francis G.J.
27eec433-a773-4cc7-8327-70c5103382e0
Essex, Jonathan W.
1f409cfe-6ba4-42e2-a0ab-a931826314b5
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Frey, Jeremy G.
ba60c559-c4af-44f1-87e6-ce69819bf23f
Longford, Francis G.J.
27eec433-a773-4cc7-8327-70c5103382e0
Essex, Jonathan W.
1f409cfe-6ba4-42e2-a0ab-a931826314b5
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Frey, Jeremy G.
ba60c559-c4af-44f1-87e6-ce69819bf23f

Longford, Francis G.J., Essex, Jonathan W., Skylaris, Chris-Kriton and Frey, Jeremy G. (2018) Surface reconstruction amendment to the intrinsic sampling method. The Journal of Chemical Physics, 149, [234705]. (doi:10.1063/1.5055241).

Record type: Article

Abstract

The intrinsic sampling method (ISM) is a powerful tool that allows the exploration of interfacial properties from molecular simulations by fitting a function that represents the local boundary between two phases. However, owing to the non-physical nature of an “intrinsic” surface, there remains an ambiguity surrounding the comparison of theoretical properties with the physical world. It is therefore important that the ISM remains internally consistent when reproducing simulated properties which match experiments, such as the surface tension or interfacial density distribution. We show that the current ISM procedure causes an over-fitting of the surface to molecules in the interface region, leading to a biased distribution of curvature at these molecular coordinates. We assert that this biased distribution is a cause of the disparity between predicted interfacial densities upon convolution to a laboratory frame, an artefact which has been known to exist since the development of the ISM. We present an improvement to the fitting procedure of the ISM in an attempt to alleviate the ambiguity surrounding the true nature of an intrinsic surface. Our “surface reconstruction” method is able to amend the shape of the interface so as to reproduce the global curvature distribution at all sampled molecular coordinates. We present the effects that this method has on the ISM predicted structure of a simulated Lennard-Jones fluid air-liquid interface. Additionally, we report an unexpected relationship between surface thermodynamic predictions of our reconstructed ISM surfaces and those of extended capillary wave theory, which is of current interest.

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Accepted/In Press date: 27 November 2018
e-pub ahead of print date: 22 December 2018

Identifiers

Local EPrints ID: 427118
URI: http://eprints.soton.ac.uk/id/eprint/427118
ISSN: 0021-9606
PURE UUID: 4e02c2a4-e289-464b-8774-49d6d8aeca95
ORCID for Jonathan W. Essex: ORCID iD orcid.org/0000-0003-2639-2746
ORCID for Chris-Kriton Skylaris: ORCID iD orcid.org/0000-0003-0258-3433
ORCID for Jeremy G. Frey: ORCID iD orcid.org/0000-0003-0842-4302

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Date deposited: 03 Jan 2019 10:29
Last modified: 18 Feb 2021 17:07

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