Dry-Surface Simulation Method for the Determination of the Work of Adhesion of Solid鈥揕iquid Interfaces

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• 作者：Fr茅d茅ric Leroy ; Florian M眉ller-Plathe
• 刊名：Langmuir
• 出版年：2015
• 出版时间：August 4, 2015
• 年：2015
• 卷：31
• 期：30
• 页码：8335-8345
• 全文大小：472K
• ISSN：1520-5827

文摘

We introduce a methodology, referred to as the dry-surface method, to calculate the work of adhesion of heterogeneous solid鈥搇iquid interfaces by molecular simulation. This method employs a straightforward thermodynamic integration approach to calculate the work of adhesion as the reversible work to turn off the attractive part of the actual solid鈥搇iquid interaction potential. It is formulated in such a way that it may be used either to evaluate the ability of force fields to reproduce reference values of the work of adhesion or to optimize force-field parameters with reference values of the work of adhesion as target quantities. The methodology is tested in the case of water on a generic model of nonpolar substrates with the structure of gold. It is validated through a quantitative comparison to phantom-wall calculations and against a previous characterization of the thermodynamics of the gold鈥搘ater interface. It is found that the work of adhesion of water on nonpolar substrates is a nonlinear function of the microscopic solid鈥搇iquid interaction energy parameter. We also comment on the ability of mean-field approaches to predict the work of adhesion of water on nonpolar substrates. In addition, we discuss in detail the information on the solid鈥搇iquid interfacial thermodynamics delivered by the phantom-wall approach. We show that phantom-wall calculations yield the solid鈥搇iquid interfacial tension relative to the solid surface tension rather than the absolute solid鈥搇iquid interfacial tension as previously believed.