We study the structure of clusters in a model colloidal system with competing interactions using Brownian dynamics simulations. A short-ranged attraction drives clustering, while a weak, long-ranged repulsion is used to model electrostatic charging in experimental systems. The former is treated with a short-ranged Morse attractive interaction, the latter with a repulsive Yukawa interaction. We consider the yield of clusters of specific structure as a function of the strength of the interactions, for clusters with m=3,4,5,6,7,10 and 13 colloids. At sufficient strengths of the attractive interaction (around 10 kT), the average bond lifetime approaches the simulation timescale and the system becomes nonergodic. For small clusters m<=5 where geometric frustration is not relevant, despite nonergodicity, for sufficient strengths of the attractive interaction the yield of clusters which maximise the number of bonds approaches 100%. However for $m=7$ and higher, in the nonergodic regime we find a lower yield of these structures where we argue geometric frustration plays a significant role. $m=6$ is a special case, where two structures, of octahedral and C2v symmetry compete, with the latter being favoured by entropic contributions in the ergodic regime and by kinetic trapping in the nonergodic regime. We believe that our results should be valid as far as the one-component description of the interaction potential is valid. A system with competing electrostatic repulsions and van der Waals attractions may be such an example. However, in some cases, the one-component description of the interaction potential may not be appropriate.
Using numerical simulations we show that a variety of novel colloidal crystalline states and multi-step melting phenomena occur on square and triangular two-dimensional periodic substrates. At half-integer fillings different kinds of frustration effects can be realized. A two-step melting transition can occur in which individual colloidal molecules initially rotate, destroying the overall orientational order, followed by the onset of interwell colloidal hopping, in good agreement with recent experiments.
Using simulations and theory, we show that the cubatic phase is metastable for three model hard platelets. The locally favored structures of perpendicular particle stacks in the fluid prevent the formation of the columnar phase through geometric frustration resulting in vitrification. Also, we find a direct link between structure and dynamic heterogeneities in the cooperative rotation of particle stacks, which is crucial for the devitrification process. Finally, we show that the life time of the glassy cubatic phase can be tuned by surprisingly small differences in particle shape.
We study the phase behaviour and the collective dynamics of interacting paramagnetic colloids assembled above a honeycomb lattice of triangular shaped magnetic minima. A frustrated colloidal molecular crystal is realized when filling these potential minima with exactly two particles per pinning site. External in-plane rotating fields are used to anneal the system into different phases, including long range ordered stripes, random fully packed loops, labyrinth and disordered states. At higher amplitude of the annealing field, the dimer lattice displays a two step melting transition where the in…
Artificial spin ice systems, namely lattices of interacting single domain ferromagnetic islands, have been used to date as microscopic models of frustration induced by lattice topology, allowing for the direct visualization of spin arrangements and textures. However, the engineering of frustrated ice states in which individual spins can be manipulated in situ and the real-time observation of their collective dynamics remain both challenging tasks. Inspired by recent theoretical advances, here we realize a colloidal version of an artificial spin ice system using interacting polarizable particle…
Geometric frustration arises when lattice structure prevents simultaneous minimization of local interactions. It leads to highly degenerate ground states and, subsequently, complex phases of matter such as water ice, spin ice and frustrated magnetic materials. Here we report a simple geometrically frustrated system composed of closely packed colloidal spheres confined between parallel walls. Diameter-tunable microgel spheres are self-assembled into a buckled triangular lattice with either up or down displacements analogous to an antiferromagnetic Ising model on a triangular lattice. Experiment…
Geometric frustration results from a discrepancy between the locally favored arrangement of the constituents of a system and the geometry of the embedding space. Geometric frustration can be either non-cumulative, which implies an extensive energy growth, or cumulative which implies super-extensive energy scaling and highly cooperative ground state configurations which may depend on the dimensions of the system. Cumulative geometric frustration was identified in a variety of continuous systems including liquid crystals, filament bundles and molecular crystals. However, a spin-lattice model whi…
Geometric frustration arises whenever the constituents of a physical assembly locally favor an arrangement that cannot be realized globally. Recently, such frustrated assemblies were shown to exhibit filamentation, size limitation, large morphological variations and other exotic response properties. While these unique characteristics can be shown to be a direct outcome of the geometric frustration, some geometrically frustrated systems do not exhibit any of the above phenomena. In this work we exploit the intrinsic approach to provide a framework for directly addressing the frustration in phys…
The resolution of geometric frustration in systems with continuous degrees of freedom often involves a cooperative inhomogeneous response and super-extensive energy scaling. In contrast, the frustration in frustrated Ising-like spin systems is resolved uniformly. In this work we bridge between these two extremes by studying a frustrated model composed of N-state spins, and varying N. The expected cooperative response, observed for large N, is strongly attenuated as N is reduced, in a non-trivial way. Moderate N values show unique topological-like phases not observed before in frustrated models…
The geometric arrangement of interacting (magnetic) dipoles is a question of fundamental importance in physics, chemistry and engineering. Motivated by recent progress concerning the self-assembly of magnetic structures, the equilibrium orientation of 8 interacting dipoles in a cubic cluster is investigated in detail. Instead of discrete equilibria we find a new type of ground state consisting of infinitely many orientations. This continuum of energetically degenerate states represents a yet unknown form of magnetic frustration. The corresponding dipole rotations in the flat potential valley o…
Bundles of filaments are subject to geometric frustration: certain deformations (e.g. bending while twisted) require longitudinal variations in spacing between filaments. While bundles are common -- from protein fibers to yarns -- the mechanical consequences of longitudinal frustration are unknown. We derive a geometrically-nonlinear formalism for bundle mechanics, using a gauge-like symmetry under reptations along filament backbones. We relate force balance to orientational geometry and assess the elastic cost of frustration in twisted toroidal bundles.
We report numerical results for the effective potential arising between two colloids immersed in a self-assembling cosolute which forms reversible clusters. The potential is evaluated at cosolute state points with different densities and temperatures but with the same connectivity properties. We find that the range of the resulting effective potential is controlled only by the cosolute thermal correlation length rather than by its connectivity length. We discuss the significant differences with previous results focused on cosolute forming irreversible clusters and we show that irreversible bon…
Geometric frustration and the ice rule are two concepts that are intimately connected and widespread across condensed matter. The first refers to the inability of a system to satisfy competing interactions in the presence of spatial constraints. The second, in its more general sense, represents a prescription for the minimization of the topological charges in a constrained system. Both can lead to manifolds of high susceptibility and non-trivial, constrained disorder where exotic behaviors can appear and even be designed deliberately. In this Colloquium, we describe the emergence of geometric …
We investigate with experiments and novel mapping the structure of a hexagonally ordered filament bundle that is held near its ends and progressively twisted around its central axis. The filaments are free to slide relative to each other and are further held under tension-free boundary conditions. Measuring the bundle packing with micro x-ray imaging, we find that the filaments develop the helical rotation $Ω$ imposed at the boundaries. We then show that the observed structure is consistent with a mapping of the filament positions to disks packed on a dual non-Euclidean surface with a Gaussian…
Granular material in a swirled container exhibits a curious transition as the number of particles is increased: at low densities the particle cluster rotates in the same direction as the swirling motion of the container, while at high densities it rotates in the opposite direction. We investigate this phenomenon experimentally and numerically using a co-rotating reference frame in which the system reaches a statistical steady-state. In this steady-state the particles form a cluster whose translational degrees of freedom are stationary, while the individual particles constantly circulate around…
We study the mechanical behavior of two-dimensional cellular tissues by formulating the continuum limit of discrete vertex models based on an energy that penalizes departures from a target area $A_0$ and a target perimeter $P_0$ for the component cells of the tissue. As the dimensionless target shape index $s_0 = \frac{P_0}{\sqrt{A_0}}$ is varied, we find a transition from a soft elastic regime for compatible target perimeter and area to a stiffer nonlinear elastic regime frustrated by geometric incompatibility. We show that the ground state in the soft regime has a family of degenerate soluti…
Geometric frustration appears in a broad range of systems, generally emerging as disordered ground configurations, thereby impeding understanding of the phenomenon's underlying mechanics. We report on a continuum system featuring locally bistable units that allows for the controlled and self-sustained manifestation of macroscopic geometric frustration. The patterning of the units encodes a finite set of ordered ground configurations (spin-ice states) and a unique family of co-existing higher-order frustrated states (spin-liquid states), which are both activated upon unit inversion. We present …
Chirality frustrates and shapes the assembly of flexible filaments in rope-like, twisted bundles and fibers by introducing gradients of both filament shape (i.e. curvature) and packing throughout the structure. Previous models of chiral filament bundle formation have shown that this frustration gives rise to several distinct morphological responses, including self-limiting bundle widths, anisotropic domain (tape-like) formation and topological defects in the lateral inter-filament order. In this paper, we employ a combination of continuum elasticity theory and discrete filament bundle simulati…
The concept of geometrical frustration in condensed matter physics refers to the fact that a system has a locally preferred structure with an energy density lower than the infinite ground state. This notion is however often used in a qualitative sense only. In this article, we discuss a quantitative definition of geometrical frustration in the context of lattice models of binary spins. To this aim, we introduce the framework of local energy landscapes, within which frustration can be quantified as the discrepancy between the energy of locally preferred structures and the ground state. Our defi…
The uniform director field obtained for the nematic ground state of the hard-rod model of liquid crystals in two dimensions reflects the high symmetry of the constituents of the liquid; It is a manifestation of the constituents' local tendency to avoid splaying and bending with respect to one another. In contrast, bent-core (or banana shaped) liquid-crystal-forming-molecules locally favor a state of zero splay and constant bend. However, such a structure cannot be realized in the plane and the resulting liquid-crystalline phase is frustrated and must exhibit some compromise of these two mutual…
We consider three popular model glassformers, the Kob-Andersen and Wahnström binary Lennard-Jones models and weakly polydisperse hard spheres. Although these systems exhibit a range of fragilities, all feature a rather similar behaviour in their local structure approaching dynamic arrest. In particular we use the dynamic topological cluster classification to extract a locally favoured structure which is particular to each system. These structures form percolating networks, however in all cases there is a strong decoupling between structural and dynamic lengthscales. We suggest that the lack of…
The effective interaction between charged colloidal particles confined between two planar like-charged walls is investigated using computer simulations of the primitive model describing asymmetric electrolytes. In detail, we calculate the effective force acting onto a single macroion and onto a macroion pair in the presence of slit-like confinement. For moderate Coulomb coupling, we find that this force is repulsive. Under strong coupling conditions, however, the sign of the force depends on the distance to the plates and on the interparticle distance. In particular, the particle-plate interac…
Geometric frustration is an approach to the glass transition based upon the consideration of locally favoured structures (LFS), which are geometric motifs which minimise the local free energy. Geometric frustration proposes that a transition to a crystalline state is frustrated because these LFS do not tile space. However, this concept is based on icosahedra which are not always the LFS for a given system. The LFS of the popular Kob-Andersen (KA) model glassformer is the bicapped square antiprism, which does tile space. Such an LFS-crystal is indeed realised in the $\mathrm{Al_{2}Cu}$ structur…
We study the designing principles of the simplest colloidal propeller, an architecture built from four identical spheres that can couple translation with rotation to produce controlled drift motion. By considering superparamagnetic beads, we show that the simultaneous action of a magnetic field and a shear flow leads to the migration of the cluster in the vorticity direction. We investigate the dependence of the migration velocity on the geometrical parameters of the cluster, and find that significant cluster separation can be achieved under the typical operation conditions of microfluidic dev…
Although buckling is a prime route to achieve functionalization and synthesis of single colloids, buckling of colloidal structures---made up of multiple colloids---remains poorly studied. Here, we investigate the buckling of the simplest form of a colloidal structure, a colloidal chain that is self-assembled through critical Casimir forces. We demonstrate that the mechanical instability of such a chain is strikingly reminiscent of that of classical Euler buckling but with thermal fluctuations and plastic effects playing a significant role. Namely, we find that fluctuations tend to diverge clos…
Controlling the self-assembly of supramolecular structures is vital for living cells, and a central challenge for engineering at the nano- and microscales. Nevertheless, even particles without optimized shapes can robustly form well-defined morphologies. This is the case in numerous medical conditions where normally soluble proteins aggregate into fibers. Beyond the diversity of molecular mechanisms involved, we propose that fibers generically arise from the aggregation of irregular particles with short-range interactions. Using a minimal model of ill-fitting, sticky particles, we demonstrate …
Helical structures are ubiquitous in nature and engineering, ranging from DNA molecules to plant tendrils, from sea snail shells to nanoribbons. While the helical shapes in natural and engineered systems often exhibit nearly uniform radius and pitch, helical shell structures with changing radius and pitch, such as seashells and some plant tendrils, adds to the variety of this family of aesthetic beauty. Here we develop a comprehensive theoretical framework for tunable helical morphologies, and report the first biomimetic seashell-like structure resulting from mechanics of geometric frustration…
We investigate the influence of geometric confinement on the free energy of an idealized model for charge-stabilized colloidal suspensions. The mean-field Poisson-Boltzmann formulation for this system predicts pure repulsion among macroionic colloidal spheres. Fluctuations in the simple ions' distribution provide a mechanism for the macroions to attract each other at large separations. Although this Casimir interaction is long-ranged, it is too weak to influence colloidal crystals' dynamics.
In many biological systems, the curvature of the surfaces cells live on influence their collective properties. Curvature should likewise influence the behavior of active colloidal particles. We show using molecular simulation of self-propelled active particles on surfaces of Gaussian curvature (both positive and negative) that curvature sign and magnitude can alter the system's collective behavior. Curvature acts as a geometrical lens and shifts the critical density of motility-induced phase separation (MIPS) to lower values for positive curvature and higher values for negative curvature, whic…
We study experimentally what is arguably the simplest yet non-trivial colloidal system: two-dimensional clusters of 6 spherical particles bound by depletion interactions. These clusters have multiple, degenerate ground states whose equilibrium distribution is determined by entropic factors, principally the symmetry. We observe the equilibrium rearrangements between ground states as well as all of the low-lying excited states. In contrast to the ground states, the excited states have soft modes and low symmetry, and their occupation probabilities depend on the size of the configuration space re…
We show that geometric confinement dramatically affects the shear-induced configurations of dense mono-disperse colloidal suspensions; a new structure emerges, where layers of particles buckle to stack in a more efficient packing. The volume fraction in the shear zone is controlled by a balance between the viscous stresses and the osmotic pressure of a contacting reservoir of unsheared particles. We present a model that accounts for our observations and helps elucidate the complex interplay between particle packing and shear stress for confined suspensions.
Multiple light scattering is widely used to characterize dense colloidal systems as well as in deep tissue imaging; experiments are often interpreted via a theory of diffusion of the light intensity within a sample, neglecting the vector nature of the electromagnetic wave. Recent experiments on diffuse backscattering with linearly polarized light from colloidal suspensions of micron size particles were found to display strong intensity variations with fourfold rotational symmetry when observed through an arbitrarily oriented linear analyzer. We show that these polarization patterns are manifes…
Filamentous bacteriophages such as fd-like viruses are monodisperse rod-like colloids that have well defined properties: diameter, length, rigidity, charge and chirality. Engineering those viruses leads to a library of colloidal rods which can be used as building blocks for reconfigurable and hierarchical self-assembly. Their condensation in aqueous solution þ{with additive polymers which act as depletants to induce} attraction between the rods leads to a myriad of fluid-like micronic structures ranging from isotropic/nematic droplets, colloid membranes, achiral membrane seeds, twisted ribbons…
