Collective interactions in the mechanism of adhesion of condensed phase nuclei to a crystal surface. 1. Spatial organization

Self-organization into domains with spontaneous polarization is revealed for an ensemble of water molecules occurring in a contact layer on a defectless polarizable crystal surface. These domains are the sources for specific heteropolarization interactions of condensed phase nuclei with a substrate. The formation of a spatially nonuniform structure is energetically advantageous due to a nonlinear dependence of polarization energy on field strength. Domain sizes equal to several nanometers are governed by the competition between the energy advantage resulting from the coalescence of the domains and the entropy gain caused by their disintegration into smaller fragments. The forces of spontaneous mutual polarization between an adsorbed film divided into domains and a polarized substrate enhance the adhesion to the surface and markedly affect the adsorption mechanism. Computer simulation of the domain formation in a film of water molecules adsorbed on the surface of crystalline silver iodide particles is implemented by the Monte Carlo method with the summation of the long-range electrostatic interactions by means of the Fourier expansion of the field potential. Comparative analysis of the collective behavior of molecules, which underlies the layer-by-layer nucleation, and the indirect signs of domain formation is performed on the basis of experimental data on polarized surfaces with a hexagonal crystalline structure.