Liquid lattice model

If the interactions are strong - and this is frequently the case for mobile ions at high concentration - a liquid lattice model suits better but is more difficult to develop theoretically. Nevertheless, numerous trials have been attempted . These models show the correlation effects between mobile ions to an advantage and in some cases, the models imply an effective potential, the form and barrier height of which depend on the mobile ion concentration 3 . 

Using the liquid lattice model in Fig. 3.8(b) it can be readily shown that the number of such contacts p is given by... 

There is, of course, a mass of rather direct evidence on orientation at the liquid-vapor interface, much of which is at least implicit in this chapter and in Chapter IV. The methods of statistical mechanics are applicable to the calculation of surface orientation of assymmetric molecules, usually by introducing an angular dependence to the inter-molecular potential function (see Refs. 67, 68, 77 as examples). Widom has applied a mean-held approximation to a lattice model to predict the tendency of AB molecules to adsorb and orient perpendicular to the interface between phases of AA and BB [78]. In the case of water, a molecular dynamics calculation concluded that the surface dipole density corresponded to a tendency for surface-OH groups to point toward the vapor phase [79]. 

Of particular interest has been the study of the polymer configurations at the solid-liquid interface. Beginning with lattice theories, early models of polymer adsorption captured most of the features of adsorption such as the loop, train, and tail structures and the influence of the surface interaction parameter (see Refs. 57, 58, 62 for reviews of older theories). These lattice models have been expanded on in recent years using modem computational methods [63,64] and have allowed the calculation of equilibrium partitioning between a poly-... 

The parameter /r tunes the stiffness of the potential. It is chosen such that the repulsive part of the Leimard-Jones potential makes a crossing of bonds highly improbable (e.g., k= 30). This off-lattice model has a rather realistic equation of state and reproduces many experimental features of polymer solutions. Due to the attractive interactions the model exhibits a liquid-vapour coexistence, and an isolated chain undergoes a transition from a self-avoiding walk at high temperatures to a collapsed globule at low temperatures. Since all interactions are continuous, the model is tractable by Monte Carlo simulations as well as by molecular dynamics. Generalizations of the Leimard-Jones potential to anisotropic pair interactions are available e.g., the Gay-Beme potential [29]. This latter potential has been employed to study non-spherical particles that possibly fomi liquid crystalline phases. 

A lattice model that takes such attractions between parallel bonds into account provides a reasonable prediction of polymer melting points [13] and of their interplay with liquid-liquid demixing in polymer solutions [14]. The same factors that favor freezing do affect to a greater or lesser extent the formation of mesophases hence, there is a close relation between polymer crystallization and the formation of mesophases, which are frequently observed before polymer crystallization (see other papers in this issue). 

The structure of a simple mixture is dominated by the repulsive forces between the molecules [15]. Any model of a liquid mixture and, a fortiori of a polymer solution, should therefore take proper account of the configurational entropy of the mixture [16-18]. In the standard lattice model of a polymer solution, it is assumed that polymers live on a regular lattice of n sites with coordination number q. If there are n2 polymer chains, each occupying r consecutive sites, then the remaining m single sites are occupied by the solvent. The total volume of the incompressible solution is n = m + m2. In the case r = 1, the combinatorial contribution of two kinds of molecules to the partition function is... 

The quality of the mean-field approximation can be tested in simulations of the same lattice model [13]. Ideally, direct free-energy calculations of the liquid and solid phases would allow us to locate the point where the two phases coexist. However, in the present studies we followed a less accurate, but simpler approach we observed the onset of freezing in a simulation where the system was slowly cooled. To diminish the effect of supercooling at the freezing point, we introduced a terraced substrate into the system to act as a crystallization seed [14]. We verified that this seed had little effect on the phase coexistence temperature. For details, see Sect. A.3. At freezing, we have... 

This chapter is concerned with the application of liquid state methods to the behavior of polymers at surfaces. The focus is on computer simulation and liquid state theories for the structure of continuous-space or off-lattice models of polymers near surfaces. The first computer simulations of off-lattice models of polymers at surfaces appeared in the late 1980s, and the first theory was reported in 1991. Since then there have been many theoretical and simulation studies on a number of polymer models using a variety of techniques. This chapter does not address or discuss the considerable body of literature on the adsorption of a single chain to a surface, the scaling behavior of polymers confined to narrow spaces, or self-consistent field theories and simulations of lattice models of polymers. The interested reader is instead guided to review articles [9-11] and books [12-15] that cover these topics. 

Monte Carlo may be used to study the lateral distribution of lipid molecules in mixed bilayers. This of course is a very challenging problem, and, to date, the only way to obtain relevant information for this is to reduce the problem to a very simplistic two-dimensional lattice model. In this case, the lipid molecules occupy a given site and can be in one of the predefined number of different states. These pre-assigned states (usually about 10 are taken), are representative conformations of lipids in the gel or in the liquid state. Each state interacts in its own way with the neighbouring molecules (sitting on neighbouring sites). Typically, one is interested in the lateral phase behaviour near the gel-to-liquid phase transition of the bilayer [69,70]. For some recent simulations of mixtures of DMPC and DSPC, see the work of Sugar [71]. 

Given the character of the water-water interaction, particularly its strength, directionality and saturability, it is tempting to formulate a lattice model, or a cell model, of the liquid. In such models, local structure is the most important of the factors determining equilibrium properties. This structure appears when the molecular motion is defined relative to the vertices of a virtual lattice that spans the volume occupied by the liquid. In general, the translational motion of a molecule is either suppressed completely (static lattice model), or confined to the interior of a small region defined by repulsive interactions with surrounding molecules (cell model). Clearly, the nature of these models is such that they describe best those properties which are structure determined, and describe poorly those properties which, in some sense, depend on the breakdown of positional and orientational correlations between molecules. 

Tijssen, R., Schoenmakers, R.J., Bohmer, M.R., Koopal, L.K., and Billiet, H.A.H., Lattice models for the description of partitioning adsorption and retention in reversed-phase liquid-chromatography, including surface and shape effects, J. Chromatogr. A, 656, 135, 1993. 

Chapter S examines various models used to describe solution and compmmd phases, including those based on random substitution, the sub-lattice model, stoichiometric and non-stoichiometric compounds and models applicable to ionic liquids and aqueous solutions. Tbermodynamic models are a central issue to CALPHAD, but it should be emphasised that their success depends on the input of suitable coefficients which are usually derived empirically. An important question is, therefore, how far it is possible to eliminate the empirical element of phase diagram calculations by substituting a treatment based on first principles, using only wave-mecbanics and atomic properties. This becomes especially important when there is an absence of experimental data, which is frequently the case for the metastable phases that have also to be considered within the framework of CALPHAD methods. 

Solution of long-chain molecules When two liquids mix to form a mixture, the entropy change is similar to that of the volume expansion, as long as the solute molecules have the same size as the solvent molecules and are randomly distributed. But when the solute forms long-chain molecules, the correct method of calculating the entropy was given by Flory. First consider a lattice model where the solvent and the solute molecules have the same volume. Let i and 2 be the number of solvent and... 

In the present article, we focus on the scaled particle theory as the theoretical basis for interpreting the static solution properties of liquid-crystalline polymers. It is a statistical mechanical theory originally proposed to formulate the equation of state of hard sphere fluids [11], and has been applied to obtain approximate analytical expressions for the thermodynamic quantities of solutions of hard (sphero)cylinders [12-16] or wormlike hard spherocylinders [17, 18]. Its superiority to the Onsager theory lies in that it takes higher virial terms into account, and it is distinctive from the Flory theory in that it uses no artificial lattice model. We survey this theory for wormlike hard spherocylinders in Sect. 2, and compare its predictions with typical data of various static solution properties of liquid-crystalline polymers in Sects. 3-5. As is well known, the wormlike chain (or wormlike cylinder) is a simple yet adequate model for describing dilute solution properties of stiff or semiflexible polymers. 

Thermodynamic descriptions of polymer systems are usually based on a rigid-lattice model published in 1941 independently by Staverman and Van Santen, Huggins and Flory where the symbol x(T) is used to express the binary interaction function [16]. Once the interaction parameter is known we can calculate the liquid liquid phase behaviour. 

Taking into account the modes in which the water can be sorbed in the resin, different models should be considered to describe the overall process. First, the ordinary dissolution of a substance in the polymer may be described by the Flory-Huggins theory which treats the random mixing of an unoriented polymer and a solvent by using the liquid lattice approach. If as is the penetrant external activity, vp the polymer volume fraction and the solvent-polymer interaction parameter, the relationship relating these variables in the case of polymer of infinite molecular weight is as follows ... 

The transition to the continuum fluid may be mimicked by a discretization of the model choosing > 1. To this end, Panagiotopoulos and Kumar [292] performed simulations for several integer ratios 1 < < 5. For — 2 the tricritical point is shifted to very high density and was not exactly located. The absence of a liquid-vapor transition for = 1 and 2 appears to follow from solidification, before a liquid is formed. For > 3, ordinary liquid-vapor critical points were observed which were consistent with Ising-like behavior. Obviously, for finely discretisized lattice models the behavior approaches that of the continuum RPM. Already at = 4 the critical parameters of the lattice and continuum RPM agree closely. From the computational point of view, the exploitation of these discretization effects may open many possibilities for methodological improvements of simulations [292], From the fundamental point of view these discretization effects need to be explored in detail. 

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