Supramolecular assemblies in liquids: structure, thermodynamics, and macroscopic properties

Abstract

Models of the structure and properties of liquid mixtures are outlined. Main attention is given to quasichemical models for the modeling of supramolecular ordering in mixtures, self-organized by H bonds, leading to a unified description of their physicochemical properties. We analyze the interrelations of thermodynamic functions (Gibbs energy, enthalpy, entropy), dielectric (permittivity) and optical properties (refractive index and its fluctuation derivatives, defining Rayleigh light scattering) of non-ideal mixtures as well as the microscopic structural, electric, and optical characteristics of the aggregates. Methods are developed in order to obtain both the integral and differential parameters of aggregation, and those provide, for the first time the backgrounds for studying the supramolecular ordering in liquids outside of the nearest coordination shells up to nanosizes. Models for describing the dynamics of supramolecular reorganization, intramolecular transitions, and energy transfer during molecular thermal motion as well as fluctuation and relaxation phenomena are considered. Applications both to pure liquids and mixtures are outlined. The supramolecular assemblies in liquids with long-range molecular correlations are established. Macroscopic manifestations of the supramolecular organization in the properties of liquids are characterized. The thermodynamic functions of aggregation are presented.