Computing the Work of Solid-Liquid Adhesion in Systems with Damped Coulomb Interactions via Molecular Dynamics: Approaches and Insights

D Surblys and F Muller-Plathe and T Ohara, JOURNAL OF PHYSICAL CHEMISTRY A, 126, 5506-5516 (2022).

DOI: 10.1021/acs.jpca.2c03934

Recently, the dry-surface method Langmuir 2016, 31, 8335???8345 has been developed to compute the work of adhesion of solid???liquid and other interfaces using molecular dynamics via thermody-namic integration. Unfortunately, when long-range Coulombic interactions are present in the interface, a special treatment is required, such as solving additional Poisson equations, which is usually not implemented in generic molecular dynamics software, or as fixing some groups of atoms in place, which is undesirable most of the time. In this work, we replace the long-range Coulombic interactions with damped Coulomb interactions, and explore several thermal integration paths. We demonstrate that regardless of the integration path, the same work of adhesion values are obtained as long as the path is reversible, but the numerical efficiency differs vastly. Simple scaling of the interactions is most efficient, requiring as little as 8 sampling points, followed by changing the Coulomb damping parameter, while modifying the Coulomb interaction cutoff length performs worst. We also demonstrate that switching long-range Coulombic interactions to damped ones results in a higher work of adhesion by about 10 mJ/m2 because of slightly different liquid molecule orientation at the solid???liquid interface, and this value is mostly unchanged for surfaces with substantially different Coulombic interactions at the solid???liquid interface. Finally, even though it is possible to split the work of adhesion into van der Waals and Coulomb components, it is known that the specific per-component values are highly dependent on the integration path. We obtain an extreme case, which demonstrates that caution should be taken even when restricting to qualitative comparison. Superscript/Subscript Available

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