Unexpected finite size effects in interfacial systems: Why bigger is not always better—Increase in uncertainty of surface tension with bulk phase width
| Autor: | Francis G. J. Longford, Chris-Kriton Skylaris, Jonathan W. Essex, Jeremy G. Frey |
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| Rok vydání: | 2018 |
| Předmět: |
Materials science
Argon 010304 chemical physics General Physics and Astronomy chemistry.chemical_element Mechanics 010402 general chemistry 01 natural sciences Surface energy Virial theorem 0104 chemical sciences Surface tension chemistry Surface-tension values 0103 physical sciences Entropy (information theory) Physical and Theoretical Chemistry Phase width |
| Zdroj: | The Journal of Chemical Physics. 148:214704 |
| ISSN: | 1089-7690 0021-9606 |
| DOI: | 10.1063/1.5025887 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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