Using isothermal-isobaric Monte Carlo simulation to study the wetting behavior of model systems

We introduce a molecular simulation method to compute the interfacial properties of model systems within the isothermal-isobaric ensemble. We use a free-energy-based approach in which Monte Carlo simulations are employed to obtain an interface potential associated with the growth of a fluid film from a solid substrate. The general method is implemented within "spreading" and "drying" frameworks. The interface potentials that emerge from these calculations provide direct access to spreading and drying coefficients. These macroscopic properties are then used to compute the liquid-vapor surface tension and the contact angle of a liquid droplet in contact with the substrate. The isothermal-isobaric ensemble provides a means to change the thickness of the fluid film adjacent to the substrate by modifying the volume of the simulation box. Molecular insertions and removals are not necessary. We introduce a framework for performing local volume change moves wherein one attempts to modify the density of a narrow region of the simulation box. We show that such moves improve the sampling efficiency of inhomogeneous systems. The approach is applied to a model system consisting of a monatomic Lennard-Jones fluid in the vicinity of a structureless substrate. Results are provided for direct spreading and drying interface potential calculations at several temperatures and substrate strengths. Expanded ensemble techniques are used to evaluate interfacial properties over a wide range of temperatures and substrate strengths. The results obtained using the isothermal-isobaric approach are compared with those previously obtained via a grand canonical approach.