Multiscale Simulation Method for Quantitative Prediction of Surface Wettability at the Atomistic Level

The solid–liquid interface is of great interest because of its highly heterogeneous character and its ubiquity in various applications. The most fundamental physical variable determining the strength of the solid–liquid interface is the solid–liquid interfacial tension, which is usually measured according to the contact angle. However, an accurate experimental measurement and a reliable theoretical prediction of the contact angle remain lacking because of many practical issues. Here, we propose a first-principles-based simulation approach to quantitatively predict the contact angle of an ideally clean surface using our recently developed multiscale simulation method of density functional theory in classical explicit solvents (DFT-CES). Using this approach, we simulate the surface wettability of a graphene and graphite surface, resulting in a reliable contact angle value that is comparable to the experimental data. From our simulation results, we find that the surface wettability is dominantly affected by the strength of the solid–liquid van der Waal’s interaction. However, we further elucidate that there exists a secondary contribution from the change of water–water interaction, which is manifested by the change of liquid structure and dynamics of interfacial water layer. We expect that our proposed method can be used to quantitatively predict and understand the intriguing wetting phenomena at an atomistic level and can eventually be utilized to design a surface with a controlled hydrophobic­(philic)­ity.