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We derive properties of self-assembling rings which can template the organization of an arbitrary colloid into any periodic symmetry in two Euclidean dimensions. By viewing this as a tiling problem, we illustrate how the shape and chemical patterning of these rings are derivable, and are explicitly reflected by the symmetry group's orbifold symbol. We performed molecular dynamics simulations to observe their self-assembly and found 5 different characteristics which could be easily rationalized on the basis of this symbol. These include systems which undergo chiral phase separation, are addressably complex, exhibit self-limiting growth into clusters, form ordered "rods" in only one-dimension akin to a smectic phase, and those from symmetry groups which are pluripotent and allow one to select rings which exhibit different behaviors. We discuss how the curvature of the ring's edges plays an integral role in achieving correct self-assembly, and illustrate how to obtain these shapes. This provides a method for patterning colloidal systems at interfaces without explicitly programming this information onto the colloid itself.

Inverse design methods are powerful computational approaches for creating colloidal systems which self-assemble into a target morphology by reverse engineering the Hamiltonian of the system. Despite this, these optimization procedures tend to yield Hamiltonians which are too complex to be experimentally realized. An alternative route to complex structures involves the use of several different components, however, conventional inverse design methods do not explicitly account for the possibility of phase separation into compositionally distinct structures. Here, we present an inverse design scheme for multicomponent colloidal systems by combining active learning with a method to directly compute their ground state phase diagrams. This explicitly accounts for phase separation and can locate stable regions of Hamiltonian parameter space which grid-based surveys are prone to miss. Using this we design low-density, binary structures with Lennard-Jones-like pairwise interactions that are simpler than in the single component case and potentially realizable in an experimental setting. This reinforces the concept that ground states of simple, multicomponent systems might be rich with previously unappreciated diversity, enabling the assembly of non-trivial structures with only few simple components instead of a single complex one.

The phenomenon of dynamic arrest, more commonly referred to as gel and glass formation, originates as particle motion slows significantly. Current understanding of gels and glasses stems primarily from dispersions of spherical particles, but much less is known about how particle shape affects dynamic arrest transitions. To better understand the effects of particle shape anisotropy on gel and glass formation, we systematically measure the rheology, particle dynamics, and static microstructure of thermoreversible colloidal dispersions of adhesive hard rods (AHR). First, the dynamic arrest transitions are mapped as a function of temperature T, aspect ratio L/D≈ 3 to 7, and volume fraction φ≈ 0.1 to 0.5. The critical gel temperature T gel and glass volume fraction φ g are determined from the particle dynamics and rheology. Second, an effective orientation-averaged, short-range attraction between rods is quantified from small-angle scattering measurements and characterized by a reduced temperature τ. Similar τ is found at low rod concentrations, indicating that rod gelation occurs at similar effective attraction strength independent of L/D. Monte Carlo simulations reveal a similar convergence in τ when rods cluster and percolate with an average bond coordination number 〈n c 〉≈ 2.4, supporting the link between physical gelation and rigidity percolation. Lastly, AHR results are mapped onto a dimensionless state diagram to compare with previous predictions of attraction-driven gels, repulsion-driven glasses, and liquid crystal phases.

Binary superlattices constructed from nano- or micron-sized colloidal particles have a wide variety of applications, including the design of advanced materials. Self-assembly of such crystals from their constituent colloids can be achieved in practice by, among other means, the functionalization of colloid surfaces with single-stranded DNA sequences. However, when driven by DNA, this assembly is traditionally premised on the pairwise interaction between a single DNA sequence and its complement, and often relies on particle size asymmetry to entropically control the crystalline arrangement of its constituents. The recently proposed "multi-flavoring" motif for DNA functionalization, wherein multiple distinct strands of DNA are grafted in different ratios to different colloids, can be used to experimentally realize a binary mixture in which all pairwise interactions are independently controllable. In this work, we use various computational methods, including molecular dynamics and Wang-Landau Monte Carlo simulations, to study a multi-flavored binary system of micron-sized DNA-functionalized particles modeled implicitly by Fermi-Jagla pairwise interactions. We show how self-assembly of such systems can be controlled in a purely enthalpic manner, and by tuning only the interactions between like particles, demonstrate assembly into various morphologies. Although polymorphism is present over a wide range of pairwise interaction strengths, we show that careful selection of interactions can lead to the generation of pure compositionally ordered crystals. Additionally, we show how the crystal composition changes with the like-pair interaction strengths, and how the solution stoichiometry affects the assembled structures.

We systematically investigate the assembly of binary multi-flavored colloidal mixtures in two dimensions. In these mixtures all pairwise interactions between species may be tuned independently. This introduces an additional degree of freedom over more traditional binary mixtures with fixed mixing rules, which is anticipated to open new avenues for directed self-assembly. At present, colloidal self-assembly into non-trivial lattices tends to require either high pressures for isotropically interacting particles, or the introduction of directionally anisotropic interactions. Here we demonstrate tunable assembly into a plethora of structures which requires neither of these conditions. We develop a minimal model that defines a three-dimensional phase space containing one dimension for each pairwise interaction, then employ various computational techniques to map out regions of this phase space in which the system self-assembles into these different morphologies. We then present a mean-field model that is capable of reproducing these results for size-symmetric mixtures, which reveals how to target different structures by tuning pairwise interactions, solution stoichiometry, or both. Concerning particle size asymmetry, we find that domains in this model's phase space, corresponding to different morphologies, tend to undergo a continuous "rotation" whose magnitude is proportional to the size asymmetry. Such continuity enables one to estimate the relative stability of different lattices for arbitrary size asymmetries. Owing to its simplicity and accuracy, we expect this model to serve as a valuable design tool for engineering binary colloidal crystals from multi-flavored components.

Trimers with one attractive bead and two repulsive beads, similar to recently synthesized trimer patchy colloids, were simulated with flat-histogram Monte Carlo methods to obtain the stable self-assembled structures for different shapes and interaction potentials. Extended corresponding states principle was successfully applied to self-assembling systems in order to approximately collapse the results for models with the same shape, but different interaction range. This helps us directly compare simulation results with previous experiment, and good agreement was found between the two. In addition, a variety of self-assembled structures were observed by varying the trimer geometry, including spherical clusters, elongated clusters, monolayers, and spherical shells. In conclusion, our results help to compare simulations and experiments, via extended corresponding states, and we predict the formation of self-assembled structures for trimer shapes that have not been experimentally synthesized.