Depletion potentials in highly size-asymmetric binary hard-sphere mixtures: Comparison of accurate simulation results with theory

Abstract

We report a detailed study, using state-of-the-art simulation and theoretical methods, of the depletion potential between a pair of big hard spheres immersed in a reservoir of much smaller hard spheres, the size disparity being measured by the ratio of diameters q=σ_s/σ_b. Small particles are treated grand canonically, their influence being parameterized in terms of their packing fraction in the reservoir, η_s^r. Two specialized Monte Carlo simulation schemes --the geometrical cluster algorithm, and staged particle insertion-- are deployed to obtain accurate depletion potentials for a number of combinations of q\leq 0.1 and η_s^r. After applying corrections for simulation finite-size effects, the depletion potentials are compared with the prediction of new density functional theory (DFT) calculations based on the insertion trick using the Rosenfeld functional and several subsequent modifications. While agreement between the DFT and simulation is generally good, significant discrepancies are evident at the largest reservoir packing fraction accessible to our simulation methods, namely η_s^r=0.35. These discrepancies are, however, small compared to those between simulation and the much poorer predictions of the Derjaguin approximation at this η_s^r. The recently proposed morphometric approximation performs better than Derjaguin but is somewhat poorer than DFT for the size ratios and small sphere packing fractions that we consider. The effective potentials from simulation, DFT and the morphometric approximation were used to compute the second virial coefficient B_2 as a function of η_s^r. Comparison of the results enables an assessment of the extent to which DFT can be expected to correctly predict the propensity towards fluid fluid phase separation in additive binary hard sphere mixtures with q\leq 0.1.