Theory of the spontaneous polarization of the adsorbed monolayer of polar molecules. The collective variables method

Abstract

The theory of the spontaneous polarization of the adsorbed monolayer of polar molecules is developed using the collective variables method. The total potential of the system is represented as the sum of the one-body and two-body interaction potentials. The one-body potential depends on the orientation of the molecular dipoles in the external electric field and on the interactions between the molecules and the substrate. The two-body potential consists of the sum of intermolecular potentials which can be separated into the “short-range” part describing the orientation-independent interaction at distances, and the long-range part dependent on both the coordinates and the orientations of the interacting species. The variation of the configurational Helmholtz free energy of the system related to the long-range orientational interactions is shown to consist of three terms describing different modes of interactions of density fluctuations: (a) neglect of particle's density fluctuation or self-consistent mean field approximation (SCMF), (b) harmonic oscillations of the particle's density-the random phases approximation (RPA), and (c) various unharmonic interactions of the fluctuation waves. In the SCMF approximation using the assumption of the multiplicative separation of the high-order distribution function the singlet distribution function is calculated and the polarization vector of the adsorbed monolayer is determined. The corrections to the singlet distribution function arising from the terms (b) and (c) of the free energy are calculated. It is shown that the spontaneous polarization of the adsorbed monolayer of polar molecules may be regarded as the first-order phase transition.