Quantum Mechanical Prediction of Wettability of Multiphase Fluids-Solid Systems at Elevated Temperature

Physiochemical insights into solid-liquid interfaces are essential for characterizing surface wettability and multiphase fluid behaviors in diverse applications. We propose a first-principles approach to predict the polar and thermal effects on wetting properties of crystalline surfaces for a variety of polar or nonpolar liquids. By directly applying the approach to multiphase systems, we simultaneously predict the macroscopic contact angles, the work of adhesion at the solid-liquid interface, and the interfacial tension at the liquid-liquid interfaces. A unique feature of our approach lies in its capability of quantifying the electrostatic interaction at the interfaces of polar liquids and solid surface. Our results reveal a linear relation between the adsorption energy and the electrostatic interaction at the solid-polar liquid interface, which provides a more effective prediction than classical surface free energy calculations. By using quantum molecular dynamics simulation, we predict the variation of surface wettability in multiphase systems at elevated temperature and validate them with experiments. This approach opens a new avenue to probe the mechanism of sophisticated wetting phenomena in multiphase systems with direct quantum mechanical simulation.