Controlling Chirality of Entropic Crystals.

Colloidal crystal structures with complexity and diversity rivaling atomic and molecular crystals have been predicted and obtained for hard particles by entropy maximization. However, thus far homochiral colloidal crystals, which are candidates for photonic metamaterials, are absent. Using Monte Carlo simulations we show that chiral polyhedra exhibiting weak directional entropic forces self-assemble either an achiral crystal or a chiral crystal with limited control over the crystal handedness. Building blocks with stronger faceting exhibit higher selectivity and assemble a chiral crystal with handedness uniquely determined by the particle chirality. Tuning the strength of directional entropic forces by means of particle rounding or the use of depletants allows for reconfiguration between achiral and homochiral crystals. We rationalize our findings by quantifying the chirality strength of each particle, both from particle geometry and potential of mean force and torque diagrams.

Metastable orientational order of colloidal discoids.

The interplay between phase separation and kinetic arrest is important in supramolecular self-assembly, but their effects on emergent orientational order are not well understood when anisotropic building blocks are used. Contrary to the typical progression from disorder to order in isotropic systems, here we report that colloidal oblate discoids initially self-assemble into short, metastable strands with orientational order­regardless of the final structure. The model discoids are suspended in a refractive index and density-matched solvent. Then, we use confocal microscopy experiments and Monte Carlo simulations spanning a broad range of volume fractions and attraction strengths to show that disordered clusters form near coexistence boundaries, whereas oriented strands persist with strong attractions. We rationalize this unusual observation in light of the interaction anisotropy imparted by the discoids. These findings may guide self-assembly for anisotropic systems in which orientational order is desired, such as when tailored mechanical properties are sought.

Generic, phenomenological, on-the-fly renormalized repulsion model for self-limited organization of terminal supraparticle assemblies.

Self-limited, or terminal, supraparticles have long received great interest because of their abundance in biological systems (DNA bundles and virus capsids) and their potential use in a host of applications ranging from photonics and catalysis to encapsulation for drug delivery. Moreover, soft, uniform colloidal aggregates are a promising candidate for quasicrystal and other hierarchical assemblies. In this work, we present a generic coarse-grained model that captures the formation of self-limited assemblies observed in various soft-matter systems including nanoparticles, colloids, and polyelectrolytes. Using molecular dynamics simulations, we demonstrate that the assembly process is self-limited when the repulsion between the particles is renormalized to balance their attraction during aggregation. The uniform finite-sized aggregates are further shown to be thermodynamically stable and tunable with a single dimensionless parameter. We find large aggregates self-organize internally into a core-shell morphology and exhibit anomalous uniformity when the constituent nanoparticles have a polydisperse size distribution.

Symmetry considerations for the targeted assembly of entropically stabilized colloidal crystals via Voronoi particles.

The relationship between colloidal building blocks and their assemblies is an active field of research. As a strategy for targeting novel crystal structures, we examine the use of Voronoi particles, which are hard, space-filling particles in the shape of Voronoi cells of a target structure. Although Voronoi particles stabilize their target structure in the limit of high pressure by construction, the thermodynamic assembly of the same structure at moderate pressure, close to the onset of crystallization, is not guaranteed. Indeed, we find that a more symmetric crystal is often preferred due to additional entropic contributions arising from configurational or occupational degeneracy. We characterize the assembly behavior of the Voronoi particles in terms of the symmetries of the building blocks as well as the symmetries of crystal structures and demonstrate how controlling the degeneracies through a modification of particle shape and field-directed assembly can significantly improve the assembly propensity.

Phase behavior of Janus colloids determined by sedimentation equilibrium.

We investigate the phase behavior of short-range interacting isotropic particles and single-patch Janus particles via simulations of sedimentation equilibrium, which allows for a rapid assessment of the equation of state and phase behavior directly from simulation. The methodology is tested against results by traditional methods and is found to yield good agreement for isotropic interactions. The method is then used to study single-patch Janus particles with different interaction strengths and patch sizes with particle area coverage greater than ∼0.63. Our results show an interplay between translational and orientational order. We observe a lamellar phase, a fluid phase and a rotator close-packed structure. The lamellar phase is shown to have a different range of stability than previously observed in simulation studies for systems of similar and longer-ranged interactions.