English

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

Statistical Mechanics 2007-05-23 v2 Soft Condensed Matter Chemical Physics

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 λ\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 τ\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=λr=\lambda in the SW case. Therefore, the equivalence is explored with the cavity function y(r)y(r). Optimization of the agreement between y\swy_{\sw} and y\shsy_{\shs} to first order in density suggests the choice for τ\tau. We have performed Monte Carlo (MC) simulations of the SW fluid for λ=1.05\lambda=1.05, 1.02, and 1.01 at several densities and temperatures TT^* such that τ=0.13\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 η\eta and τ\tau, some local discrepancies between y\swy_{\sw} and y\shsy_{\shs} exist (especially for λ=1.05\lambda=1.05), the SW data converge smoothly toward the SHS values as λ1\lambda-1 decreases. The approximate mapping y\swy\shsy_{\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\shsy_{\shs} the solution of the Percus--Yevick equation as well as the rational-function approximation, the radial distribution function g(r)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.

Keywords

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

R2 v1 2026-07-22T11:32:16.253Z