Computer simulation of macroion layering in a wedge film

The layering of macroions confined to a wedge slit formed by two uncharged hard walls is studied using a canonical Monte Carlo method combined with a simulation cell that contains both wedge-shaped slit and bath regions. The macroion solution is modeled within a one-component fluid approach that in an effective way incorporates the double layer repulsion due to simple electrolyte ions as well as the discrete nature of an aqueous solvent. The layer formation under a wedge confinement is analyzed by carrying out separate simulation runs for a set of consecutive wedge segments designed to represent a single wedge slit. As the wedge thickness progressively increases, the sequence of regions along the wedge film with distinct features of macroion layering has been established. This sequence comprises (i) a wedge region of the thickness smaller than the macroion diameter that is free of macroions; (ii) a region with a one-dimensional macroion chain along the wedge corner at a wedge thickness of a one macroion diameter; (iii) a region comprising a low-ordered macroion monolayer that extends until the wedge thickness slightly above two macroion diameters; (iv) a region comprising a pair of well-defined two-dimensional configurations of macroions segregated on each of the wedge walls; and (v) a free-of-macroions wedge region between two surface monolayers that now originates from an electrostatic repulsion imposed by the surface macroions, which is followed by (vi) a well-defined macroion monolayer film between two surface monolayers, a less defined bilayer film, a three-layer film, and so on up to the bulk solution. Once formed, the macroion surface monolayers persist for all remaining wedge thicknesses up to the bulk, forming in such a way effective charged wedge boundaries. Such a formation of the macroion surface monolayers on the uncharged confining walls is related to the haloing mechanism for regulating the stability in colloidal suspensions Tohver et al. Proc. Natl. Acad. Sci. U.S.A. 2001, 98, 8951] and is discussed as well. Finally, the estimated boundary of the free of macroion region between surface monolayers correlates well with the location of the boundary of the so-called "vacuum" phase that has been observed experimentally in an aqueous suspension of charged polystyrene spheres bounded by electrostatically repulsive glass walls Pieransky et al. Phys. Rev. Lett. 1983, 50, 900].