Stimulation of vapor nucleation on perfect and imperfect hexagonal lattice surfaces

Monte Carlo simulations of water vapor nucleation on a perfect crystal surface and on a surface with defects are performed. Mass exchange with the vapor phase is modeled by using an open ensemble. Cluster-substrate interaction is described in terms of conventional atom-atom potentials. The Hamiltonian of the system includes expressions for electrostatic, polarization, exchange, and dispersion interactions. The Gibbs free energy and work of adsorption are calculated by Monte Carlo simulation in the bicano?nical ensemble. The microscopic structure of nuclei is analyzed in terms of pair correlation functions. Periodic boundary conditions are used to simulate an infinite substrate surface. Molecule-substrate and molecule-molecule long-range electrostatic interactions are calculated by summing the Fourier harmonics of the electrostatic potential. Dispersion interactions are calculated by direct summation over layers of unit cells. Nucleation on a surface with matching structure follows a layer-by-layer mechanism. The work of adsorption per molecule of a monolayer on the substrate surface has a maximum as a function of nucleus size. The steady rate of nucleation of islands of supercritical size is evaluated. The work of adsorption per molecule for layer-by-layer film growth is an oscillating function of cluster size. As a function of layer number, it has a minimum depending on the vapor pressure. The electric field generated by a microscopic surface protrusion destroys the layered structure of the condensate and eliminates free-energy nucleation barriers. However, point lattice defects do not stimulate explosive nucleation.