How `sticky' are short-range square-well fluids?
Abstract
The aim of this work is to investigate to what extent the structural properties of a short-range square-well (SW) fluid of range 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 . 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 in the SW case. Therefore, the equivalence is explored with the cavity function . Optimization of the agreement between and to first order in density suggests the choice for . We have performed Monte Carlo (MC) simulations of the SW fluid for , 1.02, and 1.01 at several densities and temperatures such that , 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 and , some local discrepancies between and exist (especially for ), the SW data converge smoothly toward the SHS values as decreases. The approximate mapping is exploited to estimate the internal energy and structure factor of the SW fluid from those of the SHS fluid. Taking for the solution of the Percus--Yevick equation as well as the rational-function approximation, the radial distribution function 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.
Cite
@article{arxiv.cond-mat/0605347,
title = {How `sticky' are short-range square-well fluids?},
author = {Alexandr Malijevsky and Santos B. Yuste and Andres Santos},
journal= {arXiv preprint arXiv:cond-mat/0605347},
year = {2007}
}
Comments
14 pages, including 3 tables and 14 figures; v2: typo in Eq. (5.1) corrected, Fig. 14 redone, to be published in JCP