Finite-size scaling and particle size cutoff effects in phase separating polydisperse fluids

Abstract

We study the liquid-vapor phase behaviour of a polydisperse fluid using grand canonical simulations and moment free energy calculations. The strongly nonlinear variation of the fractional volume of liquid across the coexistence region prevents naive extrapolation to detect the cloud point. We describe a finite-size scaling method which nevertheless permits accurate determination of cloud points and spinodals from simulations of a single system size. By varying a particle size cutoff we find that the cloud point density is highly sensitive to the presence of rare large particles; this could affect the reproducibility of experimentally measured phase behavior in colloids and polymers.

4 Pages, 4 figures

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• Even strong energy polydispersity does not affect the average structure and dynamics of simple liquids
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• Measuring local volume fraction, long-wavelength correlations and fractionation in a phase-separating polydisperse fluid
• Phase coexistence in the hard-sphere Yukawa chain fluid with chain length polydispersity: High temperature approximation
• Weakly polydisperse systems: Perturbative phase diagrams that include the critical region