Applicability of the thermodynamic and mechanical route to Young’s equation for rigid and flexible solids: A molecular dynamics simulations study of a Lennard-Jones system model

The wetting properties of a liquid in contact with a solid are commonly described by Young's equation, which defines the relationship between the angle made by a fluid droplet onto the solid surface and the interfacial properties of the different interfaces involved. When modeling such interfacial systems, several assumptions are usually made to determine this angle of contact, such as a completely rigid solid or the use of the tension at the interface instead of the surface free energy. In this work, we perform molecular dynamics simulations of a Lennard-Jones liquid in contact with a Lennard-Jones crystal and compare the contact angles measured from a droplet simulation with those calculated using Young's equation based on surface free energy or surface stress. We analyze cases where the solid atoms are kept frozen in their positions and where they are allowed to relax and simulate surfaces with different wettability and degrees of softness. Our results show that using either surface free energy or surface stress in Young's equation leads to similar contact angles but different interfacial properties. We find that the approximation of keeping the solid atoms frozen must be done carefully, especially if the liquid can efficiently pack at the interface. Finally, we show that to correctly reproduce the measured contact angles when the solid becomes soft, the quantity to be used in Young's equation is the surface free energy only and that the error committed in using the surface stress becomes larger as the softness of the solid increases.