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A Method to Manipulate Surface Tension of a Liquid Metal via Surface Oxidation and Reduction
Published on: January 26, 2016
Unexpected finite size effects in interfacial systems: Why bigger is not always better-Increase in uncertainty of
Francis G J Longford1, Jonathan W Essex1, Chris-Kriton Skylaris1
1University of Southampton, Southampton SO17 1BJ, United Kingdom.
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 Ll/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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