Influence of polydispersity on the critical parameters of an effective potential model for asymmetric hard sphere mixtures

Abstract

We report a Monte Carlo simulation study of the properties of highly asymmetric binary hard sphere mixtures. This system is treated within an effective fluid approximation in which the large particles interact through a depletion potential (R. Roth {\em et al}, Phys. Rev. E{\bf 62} 5360 (2000)) designed to capture the effects of a virtual sea of small particles. We generalize this depletion potential to include the effects of explicit size dispersity in the large particles and consider the case in which the particle diameters are distributed according to a Schulz form having degree of polydispersity 14%. The resulting alteration (with respect to the monodisperse limit) of the metastable fluid-fluid critical point parameters is determined for two values of the ratio of the diameters of the small and large particles: $q\equiv {\sigma }_s/{\bar{\sigma }}_b=0.1$ and $q=0.05$. We find that inclusion of polydispersity moves the critical point to lower reservoir volume fractions of the small particles and high volume fractions of the large ones. The estimated critical point parameters are found to be in good agreement with those predicted by a generalized corresponding states argument which provides a link to the known critical adhesion parameter of the adhesive hard sphere model. Finite-size scaling estimates of the cluster percolation line in the one phase fluid region indicate that inclusion of polydispersity moves the critical point deeper into the percolating regime. This suggests that phase separation is more likely to be preempted by dynamical arrest in polydisperse systems.

11 pages, 10 figures

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• Depletion potentials in highly size-asymmetric binary hard-sphere mixtures: Comparison of accurate simulation results with theory
• Phase behavior of colloidal suspensions with critical solvents in terms of effective interactions
• Temperature as an external field for colloid-polymer mixtures : "quenching" by heating and "melting" by cooling
• Effect of Energy Polydispersity on the Nature of Lennard-Jones Liquids
• Three-body interactions in complex fluids: virial coefficients from simulation finite-size effects
• Monte Carlo cluster algorithm for fluid phase transitions in highly size-asymmetrical binary mixtures
• Correction of coarse-graining errors by a two-level method: application to the Asakura-Oosawa model
• Critical point for de-mixing of binary hard spheres