The growth of liquid phase nuclei on the surface of some crystals was shown to differ from that described in the classic theory of capillarity. The surface of the base face of a silver iodide crystal is completely covered with a monomolecular water film already in unsaturated vapors, and the wetting conditions of the substrate are determined by the hydrophobic properties of the film surface, but not the crystal surface itself. The mechanism by which the monomolecular film is held on the surface of crystalline silver iodide was studied by the Monte Carlo method at the molecular level. It was found that the adhesion of the film to the surface of the base face of the crystal was by hydrogen bonding with the ions of the second crystallographic layer of the substrate, and the film was thermodynamically stable even in unsaturated water vapor. The film hydrophobicity is due to the deficiency of hydrogen bond donors on its surface. The nanostructural elements on the surface of the aerosol particle can neutralize the hydrophobic properties of the film and thus serve as nucleation centers.