Water-vapor clustering on the surface of β-AgI crystal in the field of defects with a disordered structure

Аннотация

The Monte Carlo method has been employed to simulate the nucleation of condensed water phase from vapor at 260 K on a crystalline silver-iodide surface containing a defect in the form of a nanoscopic spot with a random distribution of ions. The free energy and work of formation of a nucleus have been calculated in the bicanonical ensemble at the molecular level as functions of nucleus size; computer images and spatial correlation functions of molecules have been obtained. The presence of a defect with a disordered (amorphous) structure, on the one hand, entails local destructions of a monomolecular film, but, on the other hand, shifts the onset of the adsorption process toward lower vapor pressures by several orders of magnitude. Under the conditions of a growing condensate film, the defect leads to its thermodynamic stabilization and a decrease in the barrier of the formation of subsequent layers, thereby weakening the known effect of the hydrophobicity of monomolecular films on crystalline surfaces with hexagonal structures. The factors that predetermine the abnormally high efficiency of silver-iodide particles as stimulators for atmospheric-moisture nucleation at negative Celsius temperatures seem to be the presence of extended defects on the surface of aerosol particles in combination with the hexagonal structure of their crystal lattice, the optimum magnitude of direct interactions between water molecules with ions of the crystal surface layer, and the collective domain-formation effects that result from a relatively high polarizability of iodine ions.