Molecular models, polymeric systems, Monte Carlo methods

Science is in incessant evolution it grows with more precise theories and better instrumentation. The thermodynamic theories of polymers and polymeric systems move toward atomistic considerations for isomeric species modeled mathematically by molecular dynamics or Monte Carlo methods. At the same time good mean-field theories remain valid and useful—they must be remembered not only for the historical evolution of human knowledge, but also for the very practical reason of applicability, usefulness, and as tools for the understanding of material behavior. 

Monte Carlo methods have seen important advances over the last decade. These advances have permitted calculations that just a few years ago were beyond the possibilities of molecular simulations. For conciseness, the discussion presented in this article is limited to the methodological aspects of the simulation of continuum space polymeric systems. Given the nature of this encyclopedia, cited articles have been chosen for their pedagogical and scientific value, rather than for the assignment of priorities. Little reference is made to the numerous applications that have been reported in the past. It is also important to point out that much of the literature on Monte Carlo studies of polymers has been concerned with lattice models, and that several reviews of such woric have appeared in the past. While techniques employed for either on- or off-lattice systems are, to some extent, transferable, a few recent reviews have specifically addressed some of the intricacies that arise when simulating polymers in a continuum " reference to these sources for specific topics will be made whenever appropriate. 

Experimental study of infinitely-dilute polymers Is difficult and few direct measurements have been reported for configurational properties of isolated polymers in solution. Molecular simulation offers an alternate powerful method for studying the properties of model polymeric systems, including infinitely-dilute polymers in solution. Computer simulations have been performed in several cases for examining the conformational behavior of isolated, uncharged polymers [28-30] and, on a more limited basis, for studying isolated, fu/Zy-zon/zec/polyelectrolytes [31, 32]. Hooper et al [14, 15] recently performed Monte-Carlo computer simulations for a lattice model of an isolated, partially-ionized polyelectrolyte. Here, we present some of the primary results from references 14 and 15, and discuss how these results can improve our understanding of phase behavior in aqueous/polymer systems. 

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