Heterogeneous nucleation at a wall near a wetting transition: a Monte Carlo test of the classical theory

While for a slightly supersaturated vapor the free energy barrier ΔF(hom)(*), which needs to be overcome in a homogeneous nucleation event, may be extremely large, nucleation is typically much easier at the walls of the container in which the vapor is located. While no nucleation barrier exists if the walls are wet, for incomplete wetting of the walls, described via a nonzero contact angle Θ, classical theory predicts that nucleation happens through sphere-cap-shaped droplets attracted to the wall, and their formation energy is ΔF(het)(*) = ΔF(hom)(*)f(Θ), with f(Θ) = (1-cosΘ)(2)(2+cosΘ)/4. This prediction is tested through simulations for the simple cubic lattice gas model with nearest-neighbor interactions. The attractive wall is described in terms of a local 'surface field', leading to a critical wetting transition. The variation of the contact angle with the strength of the surface field is determined by using thermodynamic integration methods to obtain the wall free energies which enter Young's equation. Obtaining the chemical potential as a function of the density for a system with periodic boundary conditions (and no walls), the droplet free energy of a spherical droplet in the bulk is obtained for a wide range of droplet radii. Similarly, ΔF(het)(*) is obtained for a system with two parallel walls. We find that the classical theory is fairly accurate if a line tension correction for the contact angle is taken into account.