title: Dry-Surface Simulation Method for the Determination of the Work of Adhesion of Solid-Liquid Interfaces.
abstract: We introduce a methodology, referred to as the dry-surface method, to calculate the work of adhesion of heterogeneous solid-liquid 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-liquid 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-water interface. It is found that the work of adhesion of water on nonpolar substrates is a nonlinear function of the microscopic solid-liquid 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-liquid interfacial thermodynamics delivered by the phantom-wall approach. We show that phantom-wall calculations yield the solid-liquid interfacial tension relative to the solid surface tension rather than the absolute solid-liquid interfacial tension as previously believed.
authors.affiliation: Eduard-Zintl-Institut für Anorganische and Physikalische Chemie and Research Cluster Center of Smart Interfaces, Technische Universität Darmstadt, , Alarich-Weiss-Strasse 4, 64287 Darmstadt, Germany.
authors.forename: Frédéric
authors.initials: F
authors.lastname: Leroy
authors.affiliation: Eduard-Zintl-Institut für Anorganische and Physikalische Chemie and Research Cluster Center of Smart Interfaces, Technische Universität Darmstadt, , Alarich-Weiss-Strasse 4, 64287 Darmstadt, Germany.
authors.forename: Florian
authors.initials: F
authors.lastname: Müller-Plathe
mesh_terms: D006046:Gold / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D013499:Surface Properties; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water; D006046:Gold