Equilibration of fluid-phase coexistence in polydisperse particle systems with short- and moderate-range depletion attractions

Gibbs ensemble Monte Carlo (GEMC) simulations have been done on polydisperse systems of particles interacting via the Asakura–Oosawa depletion potential. On restricting the range of the depletion attraction particles aggregate forming long-lived, unequilibrated structures and it becomes increasingly difficult to sample phase space. It is found that by simply equilibrating systems sequentially starting at longer ranges of attraction, the equilibrium fluid–fluid phase coexistence can be determined down to polymer-colloid size ratios approaching 10%. For such short ranges of the depletion interaction it becomes difficult to obtain reliable estimates of chemical potentials due to occasional particle insertions resulting in very low energies. The results show that full equilibrium is not reached at a polymer-colloid size ratio of 10% in spite of lengthy simulations due to persistent structures in the dense-fluid phase dominated by particles belonging to the larger size fraction. Free-volume theory with a polydisperse colloid component, modeled as a three-component mixture, is used for qualitative comparison with some of the results of the computer simulations.

Research Highlights
► Gibbs ensemble simulations of short-range attractive depletion systems.
► Direct equilibration from an initial lattice stops short of equilibrium.
► Equilibrating sequentially starting at longer ranges enables reaching shorter ranges.
► Free-volume theory with a polydisperse colloid component shows qualitative agreement.