Quenched-annealed models

A major drawback of the RFIM, however, is that it focuses entirely on the aspect of disorder, whereas confinement plays no role. To accormt for this problem, more recent theoretical studies, and computer simulations, of fluids in disordered media employ the concept of a quenched-annealed (QA) mixture [290, 291]. Here, the fluid molecules (the annealed species) equilibrate in a matrix consisting of particles quenched in a disordered (configuration. Thus, QA models combine both disorder and confinement, the latter being guaranteed by the finite size of the matrix particles. In addition, preferential adsorption can be realized by assiuning attractive (or other, more complex) interactions between fluid and matrix particles. 

In the framework of QA models, the disordered medium, such as the one depicted in Fig. 7.1, is modeled as a matrix consisting of particles. The latter are frozen in place quenched) according to a distribution where Q = Qi. denotes the set of matrix particle coordinates. 

In the simplest case (e.g., hard-sphere matrices), these quenched variables are just the particle po.sitions Ri. However, one may also consider the case of matrix particles with internal (hjgrees of freedom, sucli as a charge or an orientation. In the latter case, the coordinates are Qi = (fl. , fii), with Qi being the set of Euler angles defining the particle orientation. 

For the theoretical formalism to be described it is convenient to choose P(Q m) as an equilibrium canonical distribution established at some 

From a practical point of view, the thermal averages defined 1 Eq. (7.6) are not very meaningful as they depend on the specific realization of the matrix. Therefore one needs to supplement the thermal average by a disorder average over matrix configurations, 3delding the double average 

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Our main focus in this chapter has been on the applications of the replica Ornstein-Zernike equations designed by Given and Stell [17-19] for quenched-annealed systems. This theory has been shown to yield interesting results for adsorption of a hard sphere fluid mimicking colloidal suspension, for a system of multiple permeable membranes and for a hard sphere fluid in a matrix of chain molecules. Much room remains to explore even simple quenched-annealed models either in the framework of theoretical approaches or by computer simulation. 

Several colloidal systems, that are of practical importance, contain spherically symmetric particles the size of which changes continuously. Polydisperse fluid mixtures can be described by a continuous probability density of one or more particle attributes, such as particle size. Thus, they may be viewed as containing an infinite number of components. It has been several decades since the introduction of polydispersity as a model for molecular mixtures [73], but only recently has it received widespread attention [74-82]. Initially, work was concentrated on nearly monodisperse mixtures and the polydispersity was accounted for by the construction of perturbation expansions with a pure, monodispersive, component as the reference fluid [77,80]. Subsequently, Kofke and Glandt [79] have obtained the equation of state using a theory based on the distinction of particular species in a polydispersive mixture, not by their intermolecular potentials but by a specific form of the distribution of their chemical potentials. Quite recently, Lado [81,82] has generalized the usual OZ equation to the case of a polydispersive mixture. Recently, the latter theory has been also extended to the case of polydisperse quenched-annealed mixtures [83,84]. As this approach has not been reviewed previously, we shall consider it in some detail. 

Numerical results for the some model polydisperse systems have been reported in Refs. 81-83. It has been shown that the effect of increasing polydispersity on the number-number distribution function is that the structure decreases with increasing polydispersity. This pattern is common for the behavior of two- and three-dimensional polydisperse fluids [81] and also for three-dimensional quenched-annealed systems [83]. 

There have been other promising lines along which the theory of quenched-annealed systems has progressed recently. One of them, worth discussing in more detail, is the adsorption of fluids in inhomogeneous, i.e. geometrically restricted, quenched media [31,32]. In this area one encounters severe methodological and technical difficulties. At the moment, a set of results has been obtained at the level of a hard sphere type model adsorbed in sht-like pores with quenched distribution of hard sphere obstacles [33]. However, the problem of phase transitions has remained out of the question so far. 

The theory of quenched-annealed fluids is a rapidly developing area. In this chapter we have attempted to present some of the issues already solved and to discuss only some of the problems that need further study. Undoubtedly there remains much room for theoretical developments. On the other hand, accumulation of the theoretical and simulation results is required for further progress. Of particular importance are the data for thermodynamics and phase transitions in partly quenched, even quite simple systems. The studies of the models with more sophisticated interactions and model complex fluids, closer to the systems of experimental focus and of practical interest, are of much interest and seem likely to be developed in future. 

Let us consider a simple model of a quenched-annealed system which consists of particles belonging to two species species 0 is quenched (matrix) and species 1 is annealed, i.e., the particles are allowed to equlibrate between themselves in the presence of 0 particles. We assume that the subsystem composed of 0 particles has been a usual fluid before quenching. One can characterize it either by the density or by the value of the chemical potential The interparticle interaction Woo(r) does not need to be specified for the moment. It is just assumed that the fluid with interaction woo(r) has reached an equlibrium at certain temperature Tq, and then the fluid has been quenched at this temperature without structural relaxation. Thus, the distribution of species 0 is any one from a set of equihbrium configurations corresponding to canonical or grand canonical ensemble. We denote the interactions between annealed particles by Un r), and the cross fluid-matrix interactions by Wio(r). 

We presented a novel quenched solid non-local density functional (QSNLDFT) model, which provides a r istic description of adsorption on amorphous surfaces without resorting to computationally expensive two- or three-dimensional DFT formulations. The main idea is to consider solid as a quenched component of the solid-fluid mixture rather than a source of the external potential. The QSNLDFT extends the quenched-annealed DFT proposed recently by M. Schmidt and cowoikers [23,24] for systems with hard core interactions to porous solids with attractive interactions. We presented several examples of calculated adsorption isotherms on amorphous and microporous solids, which are in qualitative agreement with experimental measurements on typical polymer-templated silica materials like SBA-15, FDU-1 and oftiers. Introduction of the solid density distribution in QSNLDFT eliminates strong layering of the fluid near the walls that was a characteristic feature of NLDFT models with smoodi pore walls. As the result, QSNLDFT predicts smooth isotherms in the region of polymolecular adsorption. The main advantage of the proposed approach is that QSNLDFT retains one-dimensional solid and fluid density distributions, and thus, provides computational efficiency and accuracy similar to conventional NLDFT models. 

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