Unexpected finite size effects in interfacial systems: why bigger is not always better - increase in uncertainty of surface tension with bulk phase width
Unexpected finite size effects in interfacial systems: why bigger is not always better - increase in uncertainty of surface tension with bulk phase width
We present an unexpected finite size effect affecting interfacial molecular simulations that is proportional to the width-to-surface-area ratio of the bulk phase $L_l / A$. This finite size effect has a significant impact on the variance of surface tension values calculated using the virial summation method. A theoretical derivation of the origin of the effect is proposed, giving a new insight into the importance of optimising system dimensions in interfacial simulations. We demonstrate the consequences of this finite size effect via a new way to estimate the surface energetic and entropic properties of simulated air-liquid interfaces. Our method is based on macroscopic thermodynamic theory and involves comparing the internal energies of systems with varying dimensions. We present the testing of these methods using simulations of the TIP4P/2005 water forcefield and a Lennard-Jones fluid model of argon. Finally, we provide suggestions of additional situations in which this finite size effect is expected to be significant, as well as possible ways to avoid its impact.
1-12
Longford, Francis G.J.
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Essex, Jonathan W.
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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)
Unexpected finite size effects in interfacial systems: why bigger is not always better - increase in uncertainty of surface tension with bulk phase width.
The Journal of Chemical Physics, 148 (21), , [214704].
(doi:10.1063/1.5025887).
Abstract
We present an unexpected finite size effect affecting interfacial molecular simulations that is proportional to the width-to-surface-area ratio of the bulk phase $L_l / A$. This finite size effect has a significant impact on the variance of surface tension values calculated using the virial summation method. A theoretical derivation of the origin of the effect is proposed, giving a new insight into the importance of optimising system dimensions in interfacial simulations. We demonstrate the consequences of this finite size effect via a new way to estimate the surface energetic and entropic properties of simulated air-liquid interfaces. Our method is based on macroscopic thermodynamic theory and involves comparing the internal energies of systems with varying dimensions. We present the testing of these methods using simulations of the TIP4P/2005 water forcefield and a Lennard-Jones fluid model of argon. Finally, we provide suggestions of additional situations in which this finite size effect is expected to be significant, as well as possible ways to avoid its impact.
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Accepted/In Press date: 18 May 2018
e-pub ahead of print date: 5 June 2018
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Local EPrints ID: 421639
URI: http://eprints.soton.ac.uk/id/eprint/421639
ISSN: 0021-9606
PURE UUID: 3e624fa4-635f-46e3-8e0d-cd841735cf05
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Date deposited: 18 Jun 2018 16:30
Last modified: 16 Mar 2024 03:51
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Author:
Francis G.J. Longford
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