We use orientational-bias Monte Carlo simulations to examine the phase behavior of two-dimensional hard rectangles in the bulk and under confinement by hard walls. For all of the rod aspect ratios and area fractions studied, we find that confinement increases the degree of nematic ordering over the bulk, as confined rods tend to align their long axes parallel to the confining walls. The extent of nematic ordering increases as the separation between the confining walls decreases. If the aspect ratio of the rectangles is sufficiently large, they exhibit nematic ordering in both the bulk and under confinement, where the nematic director is set by the walls. Rods with a small aspect ratio are isotropic in the bulk and exhibit weak tetratic tendencies for sufficiently high densities. From studies of density profiles, angular distributions, and orientational correlation functions for confined, low-aspect-ratio rods, it is apparent that they align their long axes parallel to the wall in the near-wall region, where layering occurs for sufficiently high rod densities. However, confined rods with low aspect ratios still exhibit weak tetratic (isotropic) tendencies near the center of the confined region for all but the smallest wall separations. We note that although our studies probe the ordering of hard rectangles, the entropic tendencies that we observe here will be present for rods with energetic interactions. Thus, these studies serve as a general starting point for understanding and controlling the assembly of rods in two-dimensional confining geometries.

We investigated the ordering of gold nanowires that settled from aqueous suspension onto a glass substrate due to gravity. The nanowires, ca. 300 nm in cross-sectional diameter and ca. 2, 4, or 7 microns in length, were coated with 2-mercaptoethanesulfonic acid to provide electrostatic repulsion and prevent aggregation. The layer of nanowires in direct contact with the substrate was examined from below using optical microscopy and found to exhibit smectic-like ordering. The extent of smectic ordering depended on nanowire length with the shortest (2 μm) nanowires exhibiting the best ordering. To understand the assembly in this system, we used canonical Monte Carlo simulations to model the two-dimensional ordering of the nanowires on a substrate. We accounted for van der Waals and electrostatic interactions between the nanowires. The simulations reproduced the experimental trends and showed that roughness at the ends of the nanowires, which locally increased electrostatic repulsion, is critical to correctly predicting the experimentally observed smectic ordering.

Understanding how micro- and nanoparticles interact is important for achieving bottom-up assembly of desired structures. Here, we examine the self-assembly of two-component, compositionally asymmetric nanocylinders that sediment from solution onto a solid surface. These particles spontaneously formed smectic arrays. Within the rows of an array, nanocylinders tended to assemble such that neighboring particles had the same orientation of their segments. As a probe of interparticle interactions, we classified nanocylinder alignments by measuring the segment orientations of many sets of neighboring particles. Monte Carlo simulations incorporating an exact expression for the van der Waals (vdW) energy indicate that differences in the vdW interactions, even when small, are the key factor in producing observed segment alignment. These results point to asymmetrical vdW interactions as a potentially powerful means of controlling orientation in multicomponent cylinder arrays, and suggest that designing for these interactions could yield new ways to control self-assembly.

We use Monte Carlo simulations in two dimensions to study the depletion forces between two hard squares in a suspension of hard rods or disks. We determine the effects of size and concentration of rods and disks on the potential of mean force between the squares. Both rods and disks produce a short-range depletion attraction between the two squares. The depletion interaction can be strong enough to outweigh the (rotational) entropic repulsion between the squares at certain sizes and concentrations of the rods and disks. We also probe the relative orientation that two squares adopt as they approach each other and we observe rich behavior, in which the relative orientation depends on the size, concentration, and shape of the depletion agent. Simple models based on the ideas of Asakura and Oosawa [J. Chem. Phys. 22, 1255 (1954)] can explain trends in the potentials of mean force obtained from the simulations.