Interaction site fluids atomic theory

Over the p t several years we and our collaborators have pursued a continuous space liquid state approach to developing a computationally convenient microscopic theory of the equilibrium properties of polymeric systems. Integral equations method [5-7], now widely employed to understand structure, thermodynamics and phase transitions in atomic, colloidal, and small molecule fluids, have been generalized to treat macromolecular materials. The purpose of this paper is to provide the first comprehensive review of this work referred to collectively as Polymer Reference Interaction Site Model (PRISM) theory. A few new results on polymer alloys are also presented. Besides providing a unified description of the equilibrium properties of the polymer liquid phase, the integral equation approach can be combined with density functional and/or other methods to treat a variety of inhomogeneous fluid and solid problems. 

Theories based on the solution to integral equations for the pair correlation fiinctions are now well developed and widely employed in numerical and analytic studies of simple fluids [6]. Furtlier improvements for simple fluids would require better approximations for the bridge fiinctions B(r). It has been suggested that these fiinctions can be scaled to the same fiinctional fomi for different potentials. The extension of integral equation theories to molecular fluids was first accomplished by Chandler and Andersen [30] through the introduction of the site-site direct correlation fiinction c r) between atoms in each molecule and a site-site Omstein-Zemike relation called the reference interaction site... 

One of the most active areas of research in the statistical mechanics of interfacial systems in recent years has been the problem of freezing. The principal source of progress in this field has been the application of the classical density-functional theories (for a review of the fundamentals in these methods, see, for example, Evans ). For atomic fluids, such apphcations were pioneered by Ramakrishnan and Yussouff and subsequently by Haymet and Oxtoby and others (see, for example, Baret et al. ). Of course, such theories can also be applied to the vapor-liquid interface as well as to problems such as phase transitions in liquid crystals. Density-functional theories for these latter systems have not so far involved use of interaction site models for the intermolecular forces. 

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