Low-temperature and high-temperature approximations for penetrable-sphere fluids. Comparison with Monte Carlo simulations and integral equation theories

The two-body interaction in dilute solutions of polymer chains in good solvents can be modeled by means of effective bounded potentials, the simplest of which being that of penetrable spheres (PSs). In this paper we construct two simple analytical theories for the structural properties of PS fluids: a low-temperature (LT) approximation, that can be seen as an extension to PSs of the well-known solution of the Percus-Yevick (PY) equation for hard spheres, and a high-temperature (HT) approximation based on the exact asymptotic behavior in the limit of infinite temperature. Monte Carlo simulations for a wide range of temperatures and densities are performed to assess the validity of both theories. It is found that, despite their simplicity, the HT and LT approximations exhibit a fair agreement with the simulation data within their respective domains of applicability, so that they complement each other. A comparison with numerical solutions of the PY and the hypernetted-chain approximations is also carried out, the latter showing a very good performance, except inside the core at low temperatures.Comment: 14 pages, 8 figures; v2: some figures redone; small change

Test of a universality ansatz for the contact values of the radial distribution functions of hard-sphere mixtures near a hard wall

Recent Monte Carlo simulation results for the contact values of polydisperse hard-sphere mixtures at a hard planar wall are considered in the light of a universality assumption made in approximate theoretical approaches. It is found that the data seem to fulfill the universality ansatz reasonably well, thus opening up the possibility of inferring properties of complicated systems from the study of simpler onesComment: 9 pages, 2 figures; v2: minor changes; to be published in the special issue of Molecular Physics dedicated to the Seventh Liblice Conference on the Statistical Mechanics of Liquids (Lednice, Czech Republic, June 11-16, 2006

Communication: Inferring the equation of state of a metastable hard-sphere fluid from the equation of state of a hard-sphere mixture at high densities

A possible approximate route to obtain the equation of state of the monodisperse hard-sphere system in the metastable fluid region from the knowledge of the equation of state of a hard-sphere mixture at high densities is discussed. The proposal is illustrated by using recent Monte Carlo simulation data for the pressure of a binary mixture. It is further shown to exhibit high internal consistency.Comment: 4 pages, 2 figures; v2: Simulation data for one-component hard spheres included in Fig.

How `sticky' are short-range square-well fluids?

The aim of this work is to investigate to what extent the structural properties of a short-range square-well (SW) fluid of range $\lambda$ at a given packing fraction and reduced temperature can be represented by those of a sticky-hard-sphere (SHS) fluid at the same packing fraction and an effective stickiness parameter $\tau$. Such an equivalence cannot hold for the radial distribution function since this function has a delta singularity at contact in the SHS case, while it has a jump discontinuity at $r=\lambda$ in the SW case. Therefore, the equivalence is explored with the cavity function $y(r)$. Optimization of the agreement between y_{\sw} and y_{\shs} to first order in density suggests the choice for $\tau$. We have performed Monte Carlo (MC) simulations of the SW fluid for $\lambda=1.05$, 1.02, and 1.01 at several densities and temperatures $T^*$ such that $\tau=0.13$, 0.2, and 0.5. The resulting cavity functions have been compared with MC data of SHS fluids obtained by Miller and Frenkel [J. Phys: Cond. Matter 16, S4901 (2004)]. Although, at given values of $\eta$ and $\tau$, some local discrepancies between y_{\sw} and y_{\shs} exist (especially for $\lambda=1.05$), the SW data converge smoothly toward the SHS values as $\lambda-1$ decreases. The approximate mapping y_{\sw}\to y_{\shs} is exploited to estimate the internal energy and structure factor of the SW fluid from those of the SHS fluid. Taking for y_{\shs} the solution of the Percus--Yevick equation as well as the rational-function approximation, the radial distribution function $g(r)$ of the SW fluid is theoretically estimated and a good agreement with our MC simulations is found. Finally, a similar study is carried out for short-range SW fluid mixtures.Comment: 14 pages, including 3 tables and 14 figures; v2: typo in Eq. (5.1) corrected, Fig. 14 redone, to be published in JC

Properties of the reaction front in a reaction-subdiffusion process

We study the reaction front for the process $A+B\to C$ in which the reagents move subdiffusively. We propose a fractional reaction-subdiffusion equation in which both the motion and the reaction terms are affected by the subdiffusive character of the process. Scaling solutions to these equations are presented and compared with those of a direct numerical integration of the equations. We find that for reactants whose mean square displacement varies sublinearly with time as $\sim t^\gamma$, the scaling behaviors of the reaction front can be recovered from those of the corresponding diffusive problem with the substitution $t\to t^\gamma$Comment: Errata corrected, one reference update

Contact values of the particle-particle and wall-particle correlation functions in a hard-sphere polydisperse fluid

The contact values $g(\sigma,\sigma')$ of the radial distribution functions of a fluid of (additive) hard spheres with a given size distribution $f(\sigma)$ are considered. A ``universality'' assumption is introduced, according to which, at a given packing fraction $\eta$, $g(\sigma,\sigma')=G(z(\sigma,\sigma'))$, where $G$ is a common function independent of the number of components (either finite or infinite) and $z(\sigma,\sigma')=[2 \sigma \sigma'/(\sigma+\sigma')]\mu_2/\mu_3$ is a dimensionless parameter, $\mu_n$ being the $n$-th moment of the diameter distribution. A cubic form proposal for the $z$-dependence of $G$ is made and known exact consistency conditions for the point particle and equal size limits, as well as between two different routes to compute the pressure of the system in the presence of a hard wall, are used to express $G(z)$ in terms of the radial distribution at contact of the one-component system. For polydisperse systems we compare the contact values of the wall-particle correlation function and the compressibility factor with those obtained from recent Monte Carlo simulations.Comment: 9 pages, 7 figure