Hard-sphere fluids in annular wedges: Density distributions and depletion potentials

We analyze the density distribution and the adsorption of solvent hard spheres in an annular slit formed by two large solute spheres or a large solute and a wall at close distances by means of fundamental measure density-functional theory, anisotropic integral equations, and simulations. We find that the main features of the density distribution in the slit are described by an effective two-dimensional system of disks in the vicinity of a central obstacle. This has an immediate consequence for the depletion force between the solutes (or the wall and the solute) since the latter receives a strong line-tension contribution due to the adsorption of the effective disks at the circumference of the central obstacle. For large solute-solvent size ratios, the resulting depletion force has a straightforward geometrical interpretation which gives a precise “colloidal” limit for the depletion interaction. For intermediate size ratios of 5–10 and high solvent packing fractions larger than 0.4, the explicit density-functional results show a deep attractive well for the depletion potential at solute contact, possibly indicating demixing in a binary mixture at low solute and high solvent packing fraction besides the occurrence of gelation and freezing.