No free lunch for avoiding clustering vulnerabilities in distributed systems.

Emergent design failures are ubiquitous in complex systems, and often arise when system elements cluster. Approaches to systematically reduce clustering could improve a design's resilience, but reducing clustering is difficult if it is driven by collective interactions among design elements. Here, we use techniques from statistical physics to identify mechanisms by which spatial clusters of design elements emerge in complex systems modelled by heterogeneous networks. We find that, in addition to naive, attraction-driven clustering, heterogeneous networks can exhibit emergent, repulsion-driven clustering. We draw quantitative connections between our results on a model system in naval engineering to entropy-driven phenomena in nanoscale self-assembly, and give a general argument that the clustering phenomena we observe should arise in many distributed systems. We identify circumstances under which generic design problems will exhibit trade-offs between clustering and uncertainty in design objectives, and we present a framework to identify and quantify trade-offs to manage clustering vulnerabilities.

Nanocrystal Assemblies: Current Advances and Open Problems.

We explore the potential of nanocrystals (a term used equivalently to nanoparticles) as building blocks for nanomaterials, and the current advances and open challenges for fundamental science developments and applications. Nanocrystal assemblies are inherently multiscale, and the generation of revolutionary material properties requires a precise understanding of the relationship between structure and function, the former being determined by classical effects and the latter often by quantum effects. With an emphasis on theory and computation, we discuss challenges that hamper current assembly strategies and to what extent nanocrystal assemblies represent thermodynamic equilibrium or kinetically trapped metastable states. We also examine dynamic effects and optimization of assembly protocols. Finally, we discuss promising material functions and examples of their realization with nanocrystal assemblies.

Shape and interaction decoupling for colloidal preassembly.

Creating materials with structure that is independently controllable at a range of scales requires breaking naturally occurring hierarchies. Breaking these hierarchies can be achieved via the decoupling of building block attributes from structure during assembly. Here, we demonstrate, through computer simulations and experiments, that shape and interaction decoupling occur in colloidal cuboids suspended in evaporating emulsion droplets. The resulting colloidal clusters serve as "preassembled" mesoscale building blocks for larger-scale structures. We show that clusters of up to nine particles form mesoscale building blocks with geometries that are independent of the particles' degree of faceting and dipolar magnetic interactions. To highlight the potential of these superball clusters for hierarchical assembly, we demonstrate, using computer simulations, that clusters of six to nine particles can assemble into high-order structures that differ from bulk self-assembly of individual particles. Our results suggest that preassembled building blocks present a viable route to hierarchical materials design.

Sexual Orientation Across Porn Use, Sexual Fantasy, and In-Person Sexuality: Visualizing Branchedness and Coincidence via Sexual Configurations Theory.

Sexual orientation describes sexual interests, approaches, arousals, and attractions. People experience these interests and attractions in a number of contexts, including in-person sexuality, fantasy, and porn use, among others. The extent to which sexual orientation is divergent (branched) and/or overlapping (coincident) across these, however, is unclear. In the present study, a gender/sex and sexually diverse sample (N = 30; 15 gender/sex/ual minorities and 15 majorities) manipulated digital circles representing porn use, in-person sexuality, and fantasy on a tablet during in-person interviews. Participants used circle overlap to represent the degree of shared sexual interests across contexts and circle size to indicate the strength and/or number of sexual interests within contexts. Across multiple dimensions of sexual orientation (gender/sex, partner number, and action/behavior), we found evidence that sexual interests were both branched and coincident. These findings contribute to new understandings about the multifaceted nature of sexual orientations across contexts and provide a novel way to measure, conceptualize, and understand sexual orientation in context.

Synthesizable nanoparticle eigenshapes for colloidal crystals.

The gulf between the complexity and diversity of colloidal crystal phases predicted to form in computer simulation and that realized to date in experiment is narrowing, but is still wide. Prior work shows that many synthesized particles are far from optimal "eigenshapes" for target superlattice structures. We use digital alchemy to determine eigenshapes for possible target colloidal crystal structures for eight families of polyhedral nanoparticle shapes already synthesized in the laboratory. Within each family we predict optimal building block shapes to obtain several target superlattice structures, as a guide for future experiments. For three target crystal structures common to multiple families, we identify which of the optimal shapes is most optimal under the same thermodynamic conditions.

Particle shape tunes fragility in hard polyhedron glass-formers.

We demonstrate that fragility, a technologically relevant characteristic of glass formation, depends on particle shape for glass-formers comprised of hard polyhedral particles. We find that hard polyhedron glass-formers become stronger (less fragile) as particle shape becomes increasingly tetrahedral. We correlate fragility with local structure, and show that stronger systems display a stronger preference for a pairwise face-to-face motif that frustrates global periodic ordering and gives rise in most systems studied to bond angle distributions that are peaked around the ideal tetrahedral bond angle. We demonstrate through mean-field-like simulations of explicit particle pairs and surrounding baths of "ghost" particles that the prevalence of this pairwise configuration can be explained via free volume exchange and emergent entropic force arguments. Our study provides a clear and direct link between the local geometry of fluid structure and the properties of glass formation, independent of interaction potential or other non-geometric tuning parameters. We ultimately demonstrate that the engineering of fragility in colloidal systems via slight changes to particle shape is possible.

Publisher Correction: Robust design from systems physics.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Robust design from systems physics.

A crucial challenge in engineering modern, integrated systems is to produce robust designs. However, quantifying the robustness of a design is less straightforward than quantifying the robustness of products. For products, in particular engineering materials, intuitive, plain language terms of strong versus weak and brittle versus ductile take on precise, quantitative meaning in terms of stress-strain relationships. Here, we show that a "systems physics" framing of integrated system design produces stress-strain relationships in design space. From these stress-strain relationships, we find that both the mathematical and intuitive notions of strong versus weak and brittle versus directly characterize the robustness of designs. We use this to show that the relative robustness of designs against changes in problem objectives has a simple graphical representation. This graphical representation, and its underlying stress-strain foundation, provide new metrics that can be applied to classes of designs to assess robustness from feature- to system-level.

When does entropy promote local organization?

Crowded soft-matter and biological systems organize locally into preferred motifs. Locally-organized motifs in soft systems can, paradoxically, arise from a drive to maximize overall system entropy. Entropy-driven local order has been directly confirmed in model, synthetic colloidal systems, however similar patterns of organization occur in crowded biological systems ranging from the contents of a cell to collections of cells. In biological settings, and in soft matter more broadly, it is unclear whether entropy generically promotes or inhibits local organization. Resolving this is difficult because entropic effects are intrinsically collective, complicating efforts to isolate them. Here, we employ minimal models that artificially restrict system entropy to show that entropy drives systems toward local organization, even when the model system entropy is below reasonable physical bounds. By establishing this bound, our results suggest that entropy generically promotes local organization in crowded soft and biological systems of rigid objects.

FCC ↔ BCC Phase Transitions in Convex and Concave Hard Particle Systems.

Solid-solid transitions are ubiquitous in nature and are important for technology. Understanding and exploiting transitions are complicated by the fact that multiple transition pathways can exist between small unit cell structures such as face-centered cubic (FCC) and body-centered cubic (BCC). By symmetry, FCC ↔ BCC transitions can occur via a pair of continuous transitions or via a discontinuous, first-order transition. However, how to, or whether it is possible to, select between pathways is unclear. Here, we use particle shape change to induce FCC ↔ BCC transitions in systems where particle valence is malleable. Though some particle shapes can eliminate metastable HCP stacking faults, we find that for both convex and concave particles, transitions are first-order.

Topological order in densely packed anisotropic colloids.

The existence of topological order is frequently associated with strongly coupled quantum matter. Here, we demonstrate the existence of topological phases in classical systems of densely packed, hard, anisotropic polyhedrally shaped colloidal particles. We show that previously reported transitions in dense packings lead to the existence of topologically ordered thermodynamic phases, which we show are stable away from the dense packing limit. Our work expands the library of known topological phases, whose experimental realization could provide new means for constructing plasmonic materials that are robust in the presence of fluctuations.

The entropic bond in colloidal crystals.

A vast array of natural phenomena can be understood through the long-established schema of chemical bonding. Conventional chemical bonds arise through local gradients resulting from the rearrangement of electrons; however, it is possible that the hallmark features of chemical bonding could arise through local gradients resulting from nonelectronic forms of mediation. If other forms of mediation give rise to "bonds" that act like conventional ones, recognizing them as bonds could open new forms of supramolecular descriptions of phenomena at the nano- and microscales. Here, we show via a minimal model that crowded hard-particle systems governed solely by entropy exhibit the hallmark features of bonding despite the absence of chemical interactions. We quantitatively characterize these features and compare them to those exhibited by chemical bonds to argue for the existence of entropic bonds. As an example of the utility of the entropic bond classification, we demonstrate the nearly equivalent tradeoff between chemical bonds and entropic bonds in the colloidal crystallization of hard hexagonal nanoplates.

Engineering entropy for the inverse design of colloidal crystals from hard shapes.

Throughout the physical sciences, entropy stands out as a pivotal but enigmatic concept that, in materials design, typically takes a backseat to energy. Here, we demonstrate how to precisely engineer entropy to achieve desired colloidal crystals via particle shapes that, importantly, can be made in the laboratory. We demonstrate the inverse design of symmetric hard particles that assemble six different target colloidal crystals due solely to entropy maximization. Our approach efficiently samples 108 particle shapes from 92- and 188-dimensional design spaces to discover thermodynamically optimal shapes. We design particle shapes that self-assemble into known crystals with optimized symmetry and thermodynamic stability, as well as new crystal structures with no known atomic or other equivalent.

Phase behavior and design rules for plastic colloidal crystals of hard polyhedra via consideration of directional entropic forces.

Plastic crystals - like liquid crystals - are mesophases that can exist between liquids and crystals and possess some of the characteristic traits of each of these states of matter. Plastic crystals exhibit translational order but orientational disorder. Here, we characterize the phase behavior in systems of hard polyhedra that self-assemble plastic face-centered cubic (pFCC) colloidal crystals. We report a first-order transition from a pFCC to a body-centered tetragonal (BCT) crystal, a smooth crossover from pFCC to an orientationally-ordered FCC crystal, and an apparent orientational glass transition wherein long-range order fails to develop from a plastic crystal upon an increase in density. Using global order parameters and local environment descriptors, we describe how particle shape influences the development of orientational order with increasing density, and we provide design rules based on the arrangement of facets for engineering plastic crystal behavior in colloidal systems.

Symmetries in hard polygon systems determine plastic colloidal crystal mesophases in two dimensions.

Orientational ordering is a necessary step in the crystallization of molecules and anisotropic colloids. Plastic crystals, which are possible mesophases between the fluid and fully ordered crystal, are translationally ordered but exhibit no long range orientational order. Here, we study the two-dimensional phase behavior of hard regular polygons with edge number n = 3-12. This family of particles provides a model system to isolate the effect of shape and symmetry on the existence of plastic crystal phases. We show that the symmetry group of the particle, G, and the symmetry group of the local environment in the crystal, H, together determine plastic colloidal crystal phase behavior in two dimensions. If G contains completely the symmetry elements of H, then a plastic crystal phase is absent. If G and H share some but not all nontrivial symmetry elements, then a plastic crystal phase exists with preferred particle orientations that recover the absent symmetry elements of the crystal; we call this phase the discrete plastic crystal phase. If G and H share no nontrivial symmetry elements, then a plastic crystal phase exists without preferred orientations, which we call an indiscrete plastic crystal.

Identity crisis in alchemical space drives the entropic colloidal glass transition.

A universally accepted explanation for why liquids sometimes vitrify rather than crystallize remains hotly pursued, despite the ubiquity of glass in our everyday lives, the utilization of the glass transition in innumerable modern technologies, and nearly a century of theoretical and experimental investigation. Among the most compelling hypothesized mechanisms underlying glass formation is the development in the fluid phase of local structures that somehow prevent crystallization. Here, we explore that mechanism in the case of hard particle glasses by examining the glass transition in an extended alchemical (here, shape) space; that is, a space where particle shape is treated as a thermodynamic variable. We investigate simple systems of hard polyhedra, with no interactions aside from volume exclusion, and show via Monte Carlo simulation that glass formation in these systems arises from a multiplicity of competing local motifs, each of which is prevalent in-and predictable from-nearby ordered structures in alchemical space.

Relevance of packing to colloidal self-assembly.

Since the 1920s, packing arguments have been used to rationalize crystal structures in systems ranging from atomic mixtures to colloidal crystals. Packing arguments have recently been applied to complex nanoparticle structures, where they often, but not always, work. We examine when, if ever, packing is a causal mechanism in hard particle approximations of colloidal crystals. We investigate three crystal structures composed of their ideal packing shapes. We show that, contrary to expectations, the ordering mechanism cannot be packing, even when the thermodynamically self-assembled structure is the same as that of the densest packing. We also show that the best particle shapes for hard particle colloidal crystals at any finite pressure are imperfect versions of the ideal packing shape.

Shape-driven solid-solid transitions in colloids.

Solid-solid phase transitions are the most ubiquitous in nature, and many technologies rely on them. However, studying them in detail is difficult because of the extreme conditions (high pressure/temperature) under which many such transitions occur and the high-resolution equipment needed to capture the intermediate states of the transformations. These difficulties mean that basic questions remain unanswered, such as whether so-called diffusionless solid-solid transitions, which have only local particle rearrangement, require thermal activation. Here, we introduce a family of minimal model systems that exhibits solid-solid phase transitions that are driven by changes in the shape of colloidal particles. By using particle shape as the control variable, we entropically reshape the coordination polyhedra of the particles in the system, a change that occurs indirectly in atomic solid-solid phase transitions via changes in temperature, pressure, or density. We carry out a detailed investigation of the thermodynamics of a series of isochoric, diffusionless solid-solid phase transitions within a single shape family and find both transitions that require thermal activation or are "discontinuous" and transitions that occur without thermal activation or are "continuous." In the discontinuous case, we find that sufficiently large shape changes can drive reconfiguration on timescales comparable with those for self-assembly and without an intermediate fluid phase, and in the continuous case, solid-solid reconfiguration happens on shorter timescales than self-assembly, providing guidance for developing means of generating reconfigurable colloidal materials.

Biomimetic Hierarchical Assembly of Helical Supraparticles from Chiral Nanoparticles.

Chiroptical materials found in butterflies, beetles, stomatopod crustaceans, and other creatures are attributed to biocomposites with helical motifs and multiscale hierarchical organization. These structurally sophisticated materials self-assemble from primitive nanoscale building blocks, a process that is simpler and more energy efficient than many top-down methods currently used to produce similarly sized three-dimensional materials. Here, we report that molecular-scale chirality of a CdTe nanoparticle surface can be translated to nanoscale helical assemblies, leading to chiroptical activity in the visible electromagnetic range. Chiral CdTe nanoparticles coated with cysteine self-organize around Te cores to produce helical supraparticles. D-/L-Form of the amino acid determines the dominant left/right helicity of the supraparticles. Coarse-grained molecular dynamics simulations with a helical pair-potential confirm the assembly mechanism and the origin of its enantioselectivity, providing a framework for engineering three-dimensional chiral materials by self-assembly. The helical supraparticles further self-organize into lamellar crystals with liquid crystalline order, demonstrating the possibility of hierarchical organization and with multiple structural motifs and length scales determined by molecular-scale asymmetry of nanoparticle interactions.

Clusters of polyhedra in spherical confinement.

Dense particle packing in a confining volume remains a rich, largely unexplored problem, despite applications in blood clotting, plasmonics, industrial packaging and transport, colloidal molecule design, and information storage. Here, we report densest found clusters of the Platonic solids in spherical confinement, for up to [Formula: see text] constituent polyhedral particles. We examine the interplay between anisotropic particle shape and isotropic 3D confinement. Densest clusters exhibit a wide variety of symmetry point groups and form in up to three layers at higher N. For many N values, icosahedra and dodecahedra form clusters that resemble sphere clusters. These common structures are layers of optimal spherical codes in most cases, a surprising fact given the significant faceting of the icosahedron and dodecahedron. We also investigate cluster density as a function of N for each particle shape. We find that, in contrast to what happens in bulk, polyhedra often pack less densely than spheres. We also find especially dense clusters at so-called magic numbers of constituent particles. Our results showcase the structural diversity and experimental utility of families of solutions to the packing in confinement problem.