Phase behavior of a fluid with competing attractive and repulsive interactions

Andrew J. Archer and Nigel B. Wilding
Phys. Rev. E 76, 031501 – Published 4 September 2007

Abstract

Fluids in which the interparticle potential has a hard core, is attractive at moderate separations, and repulsive at large separations are known to exhibit unusal phase behavior, including stable inhomogeneous phases. Here we report a joint simulation and theoretical study of such a fluid, focusing on the relationship between the liquid-vapor transition line and any new phases. The phase diagram is studied as a function of the amplitude of the attraction for a certain fixed amplitude of the long ranged repulsion. We find that the effect of the repulsion is to substitute the liquid-vapor critical point and a portion of the associated liquid-vapor transition line, by two first-order transitions. One of these transitions separates the vapor from a fluid of spherical liquidlike clusters; the other separates the liquid from a fluid of spherical voids. At low temperature, the two transition lines intersect one another and a vapor-liquid transition line at a triple point. While most integral equation theories are unable to describe the new phase transitions, the Percus-Yevick approximation does succeed in capturing the vapor-cluster transition, as well as aspects of the structure of the cluster fluid, in reasonable agreement with the simulation results.

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  • Received 5 June 2007

DOI:https://doi.org/10.1103/PhysRevE.76.031501

©2007 American Physical Society

Authors & Affiliations

Andrew J. Archer1,2 and Nigel B. Wilding2

  • 1Department of Mathematical Sciences, Loughborough University, Loughborough LE11 3TU, United Kingdom
  • 2Department of Physics, University of Bath, Bath BA2 7AY, United Kingdom

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Issue

Vol. 76, Iss. 3 — September 2007

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