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Dynamics that are microscopic in space and time, so-called excitations, are considered the elementary unit of relaxation in the Dynamic Facilitation (DF) theory of the glass transition. Meanwhile, geometric motifs known as locally favored structures (LFS) are associated with vitrification in many glassformers. Recent work indicates that the probability of particles both found in locally favored structures (LFS) and excitations decreases significantly upon supercooling suggesting that there is an anti-correlation between them. [Ortlieb et al, Nature Commun. 14, 2621 (2023)]. However, the spatial relationship between excitations and LFS remains unclear. By employing state-of-the-art GPU computer simulations and colloid experiments, we analyze this relationship between LFS and excitations in model glassformers. We demonstrate that there is a spatial separation between the two in deeply supercooled liquids. This may be due to the fact that LFS are well-packed, thus they are solid and stable.

We study creep flow and yielding of particulate depletion gels under constant shear stress, combining data on different length and time scales. We characterise the breakage of meso-scale strands in the gel. Breakage events are distributed homogeneously in space, corresponding to macroscopically ductile flow. At the microscale, a spatio-temporal analysis of structural and mechanical metrics connects properties of strands before and after they fail, indicating that strand breakage is statistically predictable. Using results from different scales, we discuss the interplay between creeping and aging dynamics, and we demonstrate a viscosity bifurcation., Comment: 13 pages

Colloids can acquire a dipolar interaction in the presence of an external electric field. At high field strength, the particles form strings in the field direction. However at weaker field strength, competition with isotropic interactions is expected. One means to investigate this interplay between dipolar and isotropic interactions is to consider clusters of such particles. We have therefore identified, using the GMIN basinhopping tool, a rich library of lowest energy clusters of a dipolar colloidal system where the dipole orientation is fixed with respect to the z-axis, and the dipole strength is varied for m--membered clusters of 7 <= m <=13. In the regime where the isotropic and dipolar interactions are comparable, we find elongated polytetrahedral, octahedral and spiral clusters as well as a set of non--rigid clusters which emerge close to the transition to strings. We further implement a search algorithm which identifies these minimum energy clusters in bulk systems using the topological cluster classification [J. Chem. Phys. 139 234506 (2013)]. We demonstrate this methodology with computer simulations which shows instances of these clusters as a function of dipole strength., Comment: 11 pages

We study an intriguing new type of self-assembled active colloidal polymer system in 3D. It is obtained from a suspension of Janus particles in an electric field that induces parallel dipoles in the particles as well as self-propulsion in the plane perpendicular to the field. At low packing fractions, in experiment, the particles self-assemble into 3D columns that are self-propelled in 2D. Explicit numerical simulations combining dipolar interactions and active self-propulsion find an activity dependent transition to a string phase by increasing dipole strength. We classify the collective dynamics of strings as a function of rotational and translational diffusion. Using an anisotropic version of the Rouse model of polymers with active driving, we analytically compute the strings' collective dynamics and centre of mass motion, which matches simulations and is consistent with experimental data. We also discover long range correlations of the fluctuations along the string contour that grow with the active persistence time, a purely active effect that disappears in the thermal limit., Comment: 6 pages, 4 figures

Active solids emerge from self-actuating components interacting with each other to form crystalline patterns. In equilibrium, commensurability underpins our understanding of nanoscale friction and particle-level dynamics of crystals. However, these concepts have yet to be imported into the realm of active matter. Here, we develop an experimental platform and a theoretical description for microscopic clusters composed of active particles confined and self-assembled into small crystals. In our experiments, these crystallites form upon circular confinement of active rollers, with a magic number of 61 rollers per well. Competition between solidity and self propulsion leads to self shearing and complex flow inversion behaviour, along with self sliding states and activity induced melting. We discover active stick slip dynamics, which periodically switch between a commensurate static state and an incommensurate self-sliding state characterised by a train of localised defects. We describe the steady state behaviour using a discretised model of active hydrodynamics. We then quantify the intermittent stick slip dynamics using a self-propelled extension of the Frenkel Kontorova (FK) model, a fundamental workhorse of slipping and flow in crystals. Our findings in a colloidal model system point to a wealth of phenomena in incommensurate active solids as design principles for both assembly and robotics down to the nanoscale.

The simplicity of hard spheres as a model system is deceptive. Although the particles interact solely through volume exclusion, that nevertheless suffices for a wealth of static and dynamical phenomena to emerge, making the model an important target for achieving a comprehensive understanding of matter. In addition, while real colloidal suspensions are typically governed by complex interactions, Pusey and Van Megen [Nature 320 340--342 (1986)] demonstrated that suitably tuned suspensions result in hard-sphere like behavior, thus bringing a valuable experimental complement to the celebrated theoretical model. Colloidal hard spheres are thus both a material in their own right and a platform upon which phenomena exhibited by simple materials can be explored in great detail. These various purposes enable a particular synergy between experiment, theory and computer simulation. Here we review the extensive body of work on hard spheres, ranging from their equilibrium properties such as phase behavior, interfaces and confinement to some of the non--equilibrium phenomena they exhibit such as sedimentation, glass formation and nucleation., Comment: 97 pages

Glasses obtained from vapor deposition on a cold substrate have superior thermodynamic and kinetic stability with respect to ordinary glasses. Here we perform molecular dynamics simulations of vapor deposition of a model glass-former and investigate the origin of its high stability compared to that of ordinary glasses. We find that the vapor deposited glass is characterized by locally favoured structures (LFS) whose occurrence correlates with its stability, reaching a maximum at the optimal deposition temperature. The formation of LFS is enhanced near the free surface, hence supporting the idea that the stability of vapor deposited glasses is connected to the relaxation dynamics at the surface., Comment: Accepted for publication in Phys. Rev. Lett. (https://journals.aps.org/prl/accepted/7a07bY5cL7816472348d41f9d096a93c4bb5f035b) Transfer of copyright provided to the American Physical Society (APS)

The transport of active particles may occur in complex environments, in which it emerges from the interplay between the mobility of the active components and the quenched disorder of the environment. Here we explore structural and dynamical properties of Active Brownian Particles (ABPs) in random environments composed of fixed obstacles in three dimensions. We consider different arrangements of the obstacles. In particular, we consider two particular situations corresponding to experimentally realizable settings. Firstly, we model pinning particles in (non--overlapping) random positions and secondly in a percolating gel structure, and provide an extensive characterization of the structure and dynamics of ABPs in these complex environments. We find that the confinement increases the heterogeneity of the dynamics, with new populations of absorbed and localized particles appearing close to the obstacles. This heterogeneity has a profound impact on the motility induced phase separation (MIPS) exhibited by the particles at high activity, ranging from nucleation and growth in random disorder to a complex phase separation in porous environments.

Colloidal particles self assemble into a wide range of structures under external AC electric fields due to induced dipolar interactions [Yethiraj and Van Blaaderen Nature 421 513 (2003)]. As a result of these dipolar interactions, at low volume fraction the system is modulated between a hard-sphere like state (in the case of zero applied field) and a "string fluid" upon application of the field. Using both particle-resolved experiments and Brownian dynamics simulations, we investigate the emergence of the string fluid with a variety of structural measures including two-body and higher-order correlations. The higher-order structure we probe using three-body spatial correlation functions and a many-body approach based on minimum energy clusters of a dipolar-Lennard-Jones system. This yields a series of geometrically distinct minimum energy clusters upon increasing the strength of the dipolar interaction, which are echoed in the higher-order structure of the colloidal fluids we study here. We find good agreement between experiment and simulation at the two-body level, although some discrepancies are found at higher field strength, where the system falls out of equilibrium. Higher-order correlations exhibit reasonable agreement between experiment and simulation, again with more discrepancy at higher field strength for three--body correlation functions. At higher field strength, the cluster population in our experiments and simulations is dominated by the minimum energy clusters for all sizes $8 \leq m \leq 12$. The agreement that we find here is notable considering that there is no fit parameter in our mapping between experiment and simulation., Comment: 16 pages 7 figures

Colloidal gels consist of percolating networks of interconnected arms. Their mechanical properties depend on the individual arms, and on their collective behaviour. We use numerical simulations to pull on a single arm, built from a model colloidal gel-former with short-ranged attractive interactions. Under elongation, the arm breaks by a necking instability. We analyse this behaviour at three different length scales: a rheological continuum model of the whole arm; a microscopic analysis of the particle structure and dynamics; and the local stress tensor. Combining these different measurements gives a coherent picture of the necking and failure: the neck is characterised by plastic flow that occurs for stresses close to the arm's yield stress. The arm has an amorphous local structure and has large residual stresses from its initialisation. We find that neck formation is associated with increased plastic flow, a reduction in the stability of the local structure, and a reduction in the residual stresses; this indicates that {the} system loses its solid character and starts to behave more like a viscous fluid. We discuss the implications of these results for the modelling of gel dynamics., Comment: 15 pages

Combining experimental observations of Quincke roller clusters with computer simulations and a stability analysis, we explore the formation and stability of two interlocked self-propelled dumbbells. For large self-propulsion and significant geometric interlocking, there is a stable joint spinning motion of two dumbbells. The spinning frequency can be tuned by the self-propulsion speed of a single dumbbell, which is controlled by an external electric field for the experiments. For typical experimental parameters the rotating pair is stable with respect to thermal fluctuations but hydrodynamic interactions due to the rolling motion of neighboring dumbbells leads to a break-up of the pair. Our results provide a general insight into the stability of spinning active colloidal molecules which are geometrically locked., Comment: 5 Figures

We highlight certain key achievements in experimental work on molecular, colloidal and granular glassformers. This short review considers these three classes of experimental systems and focusses largely on the work of the authors and their coworkers and thus is far from exhaustive. Our goal is rather to discuss particular experimental results from these classes and to explore universality and specificity across the broad range of length- and time-scales they span. We emphasize that a variety of phenomena, not least dynamical heterogeneity, growing lengthscales and a change in structure, albeit subtle, are now well established in these three classes of glassformer. We then review some experimental measurements which depend more specifically on the class of glassformer, such as the Gardner transition and some which have been investigated more in one or two classes than in all, such as configurational entropy and evidence for a dynamical phase transition. We finally put forward some open questions and consider what could be done to fill some of the gaps between theoretical approaches and experiments., Comment: 32 pages, 13 figures

It is widely believed that the emergence of slow glassy dynamics is encoded in a material's microstructure. First-principles theory [mode-coupling theory (MCT)] is able to predict the dramatic slowdown of the dynamics from only static two-point correlations as input, yet it cannot capture all of the observed dynamical behavior. Here we go beyond two-point spatial correlation functions by extending MCT systematically to include higher-order static and dynamic correlations. We demonstrate that only adding the static triplet direct correlations already qualitatively changes the predicted glass-transition diagram of binary hard spheres and silica. Moreover, we find a non-trivial competition between static triplet correlations that work to stabilize the glass state, and dynamic higher-order correlations which destabilize it for both materials. We conclude that the conventionally neglected static triplet direct correlations as well as higher-order dynamic correlations are in fact non-negligible in both fragile and strong glassformers., Comment: 2 figures, accepted for publication in Physical Review Letters

Colloids may be treated as `big atoms' so that they are good models for atomic and molecular systems. Colloidal hard disks are therefore good models for 2d materials and although their phase behavior is well characterized, rheology has received relatively little attention. Here we exploit a novel, particle-resolved, experimental set-up and complementary computer simulations to measure the shear rheology of quasi-hard-disc colloids in extreme confinement. In particular, we confine quasi-2d hard discs in a circular `corral' comprised of 27 particles held in optical traps. Confinement and shear suppress hexagonal ordering that would occur in the bulk and create a layered fluid. We measure the rheology of our system by balancing drag and driving forces on each layer. Given the extreme confinement, it is remarkable that our system exhibits rheological behavior very similar to unconfined 2d and 3d hard particle systems, characterized by a dynamic yield stress and shear-thinning of comparable magnitude. By quantifying particle motion perpendicular to shear, we show that particles become more tightly confined to their layers with no concomitant increase in density upon increasing shear rate. Shear thinning is therefore a consequence of a reduction in dissipation due to a weakening in interactions between layers as the shear rate increases. We reproduce our experiments with Brownian Dynamics simulations with Hydrodynamic Interactions (HI) included at the level of the Rotne-Prager tensor. That the inclusion of HI is necessary to reproduce our experiments is evidence of their importance in transmission of momentum through the system., Comment: accepted in J. Chem. Phys. special issue on Slow Dynamics, 15 pages

Self-organisation is the spontaneous emergence of spatio-temporal structures and patterns from the interaction of smaller individual units. Examples are found across many scales in very different systems and scientific disciplines, from physics, materials science and robotics to biology, geophysics and astronomy. Recent research has highlighted how self-organisation can be both mediated and controlled by confinement. Confinement occurs through interactions with boundaries, and can function as either a catalyst or inhibitor of self-organisation. It can then become a means to actively steer the emergence or suppression of collective phenomena in space and time. Here, to provide a common framework for future research, we examine the role of confinement in self-organisation and identify overarching scientific challenges across disciplines that need to be addressed to harness its full scientific and technological potential. This framework will not only accelerate the generation of a common deeper understanding of self-organisation but also trigger the development of innovative strategies to steer it through confinement, with impact, e.g., on the design of smarter materials, tissue engineering for biomedicine and crowd management.

Colloidal dispersions are prized as model systems to understand basic properties of materials, and are central to a wide range of industries from cosmetics to foods to agrichemicals. Among the key developments in using colloids to address challenges in condensed matter is to resolve the particle coordinates in 3D, allowing a level of analysis usually only possible in computer simulation. However in amorphous materials, relating mechanical properties to microscopic structure remains problematic. This makes it rather hard to understand, for example, mechanical failure. Here we address this challenge by studying the contacts and the forces between particles, as well as their positions. To do so, we use a colloidal model system (an emulsion) in which the interparticle forces and local stress can be linked to the microscopic structure. We demonstrate the potential of our method to reveal insights into the failure mechanisms of soft amorphous solids by determining local stress in a colloidal gel. In particular, we identify `force chains' of load-bearing droplets, and local stress anisotropy, and investigate their connection with locally rigid packings of the droplets., Comment: 12 pages

Nucleation plays a critical role in the birth of crystals and is associated with a vast array of phenomena such as protein crystallization and ice formation in clouds. Despite numerous experimental and theoretical studies, many aspects of the nucleation process like the polymorph selection mechanism in the early stages are far from being understood. Here, we show that the excess of particles in a face-centred-cubic (fcc)-like environment with respect to those in a hexagonal-close-packed (hcp)-like environment in a crystal nucleus of hard spheres as observed in simulations and experiments can be explained by the higher order structure in the fluid phase. We show using both simulations and experiments that, in the metastable fluid phase, fivefold symmetry clusters -- pentagonal bipyramids (PBs) -- known to be inhibitors of crystal nucleation, transform into a different cluster -- Siamese dodecahedra (SDs). Due to their geometry, these clusters form a bridge between the fivefold symmetric fluid and the fcc crystal, thus lowering its interfacial free energy with respect to the hcp crystal, and shedding new light on the polymorph selection mechanism., Comment: Main: 4 figures SI: 5 figures

We explore crystallisation and polymorph selection in active Brownian particles with numerical simulation. In agreement with previous work [Wysocki $\textit{et al.}$ $\textit{Europhys. Lett.}$, $\textbf{105}$ 48004 (2014)], we find that crystallisation is suppressed by activity and occurs at higher densities with increasing $P\'{e}clet$ number ($Pe$). While the nucleation rate decreases with increasing activity, the crystal growth rate increases due to the accelerated dynamics in the melt. As a result of this competition we observe the transition from a nucleation and growth regime at high $Pe$ to "spinodal nucleation" at low $Pe$. Unlike the case of passive hard spheres, where preference for FCC over HCP polymorphs is weak, activity causes the annealing of HCP stacking faults, thus strongly favouring the FCC symmetry at high $Pe$. When freezing occurs more slowly, in the nucleation and growth regime, this tendency is much reduced and we see a trend towards the passive case of little preference for either polymorph., Comment: 9 pages, 6 figures

Active matter systems may be characterised by the conversion of energy into active motion, e.g. the self-propulsion of microorganisms. Artificial active colloids form models which exhibit essential properties of more complex biological systems but are amenable to laboratory experiments. While most experimental models consist of spheres, such as Janus particles, active particles of different shapes are less understood. In particular, interactions between such active colloidal "molecules" are largely unexplored. Here, we investigate the motion of active colloidal molecules and the interactions between them. We focus on self-assembled dumbbells and trimers powered by an external electric field. For dumbbells, we observe an activity-dependent behaviour of spinning, circular and orbital motion. Moreover, collisions between dumbbells lead to the hierarchical self-assembly of tetramers and hexamers, both of which form rotational excited states. On the other hand, trimers exhibit a novel type of flipping motion that leads to trajectories reminiscent of a honeycomb lattice., Comment: 8 pages, 4 figures

While proteins have been treated as particles with a spherically symmetric interaction, of course in reality the situation is rather more complex. A simple step towards higher complexity is to treat the proteins as non--spherical particles and that is the approach we pursue here. We investigate the phase behavior of enhanced green fluorescent protein (eGFP) under the addition of a non--adsorbing polymer, polyethylene glycol (PEG). From small angle x-ray scattering we infer that the eGFP undergoes dimerization and we treat the dimers as spherocylinders with aspect ratio $L/D-1 = 1.05$. Despite the complex nature of the proteins, we find that the phase behaviour is similar to that of hard spherocylinders with ideal polymer depletant, exhibiting aggregation and, in a small region of the phase diagram, crystallization. By comparing our measurements of the onset of aggregation with predictions for hard colloids and ideal polymers [S.V. Savenko and M. Dijkstra, J. Chem. Phys 124, 234902 (2006) and F. lo Verso et al., Phys. Rev. E 73, 061407 (2006)] we find good agreement, which suggests that the eGFP proteins are consistent with hard spherocylinders and ideal polymer., Comment: 12 pages

Colloidal gels constitute an important class of materials found in many contexts and with a wide range of applications. Yet as matter far from equilibrium, gels exhibit a variety of time-dependent behaviours, which can be perplexing, such as an increase in strength prior to catastrophic failure. Remarkably, such complex phenomena are faithfully captured by an extremely simple model - "sticky spheres". Here we review progress in our understanding of colloidal gels made through the use of real space analysis and particle resolved studies. We consider the challenges of obtaining a suitable experimental system where the refractive index and density of the colloidal particles is matched to that of the solvent. We review work to obtain a particle-level mechanism for rigidity in gels and the evolution of our understanding of time-dependent behaviour, from early-time aggregation to ageing, before considering the response of colloidal gels to deformation and then move on to more complex systems of anisotropic particles and mixtures. Finally we note some more exotic materials with similar properties., Comment: 55 pages, submitted to J. Phys.: Condens. Matter

Among the challenges in discriminating between theoretical approaches to the glass transition is obtaining suitable data. In particular, particle--resolved data in liquids supercooled past the mode--coupling crossover has until recently been hard to obtain. Here we combine nano-particle resolved experiments and GPU simulation data which addresses this and investigate the predictions of differing theoretical approaches. We find support for both dynamic facilitation and thermodynamic approaches. In particular, excitations, the elementary units of relaxation in dynamic facilitation theory follow the predicted scaling behaviour and the properties of cooperatively rearranging regions (CRRs) are consistent with RFOT theory. At weak supercooling there is limited correlation between particles identified in excitations and CRRs, but this increases very substantially at deep supercooling. We identify a timescale related to the CRRs which is coupled to the structural relaxation time and thus decoupled from the excitation timescale, which remains microscopic., Comment: 10 pages

We study in this paper the possible existence of Roskilde-simple liquids and their isomorphs in a rough-wall nanoconfinement. Isomorphs are curves in the thermodynamic phase diagram along which structure and dynamics are invariant in suitable nondimensionalized units. Two model liquids using molecular dynamics computer simulations are considered: the single-component Lennard-Jones (LJ) liquid and the Kob-Andersen binary LJ mixture, both of which in the bulk phases are known to have isomorphs. Nanoconfinement is implemented by adopting a slit-pore geometry with fcc crystalline walls; this implies inhomogenous density profiles both parallel and perpendicular to the confining walls. Despite this fact and consistent with an earlier study [Ingebrigtsen et. al, Phys. Rev. Lett. 111, 235901 (2013)] we find that these nanoconfined liquids have isomorphs to a good approximation. More specifically, we show good scaling of inhomogenous density profiles, mean-square displacements, and higher-order structures probed using the topological cluster classification algorithm along the isomorphs. From this study, we conjecture that in experiments, Roskilde-simple liquids may exhibit isomorphs if confined in a suitable manner, for example with carbon nanotubes. Our study thus provides an alternative framework for understanding nanoconfined liquids., Comment: 21 pages

In the COVID-19 pandemic, billions are wearing face masks, in both health care settings and in public. Which type of mask we should wear in what situation, is therefore important. There are three basic types: cotton, surgical, and respirators (e.g. FFP2, N95 and similar). All are essentially air filters worn on the face. Air filtration is relatively well understood, however, we have almost no direct evidence on the relative role played by aerosol particles of differing sizes in disease transmission. But if the virus concentration is assumed independent of aerosol particle size, then most virus will be in particles > 1 $\mu$m. We develop a model that predicts surgical masks are effective at reducing the risk of airborne transmission because the filtering material most surgical masks use is highly effective at filtering particles with diameters > 1 $\mu$m. However, surgical masks are significantly less effective than masks of FFP2, N95 and similar standards, mostly due to the poor fit of surgical masks. Earlier work found that ~30% of the air bypasses a surgical mask and is not filtered. This highlights the fact that standards for surgical masks do not specify how well the mask should fit, and so are not adequate for protection against COVID-19., Comment: 11 pages + references, 7 figures. Resubmitted version with substantial additions over original

Understanding relaxation of supercooled fluids is a major challenge and confining such systems can lead to bewildering behaviour. Here we exploit an optically confined colloidal model system in which we use reduced pressure as a control parameter. The dynamics of the system are ``Arrhenius'' at low and moderate pressure, but at higher pressures relaxation is faster than expected. We associate this faster relaxation with a decrease in density adjacent to the confining boundary due to local ordering in the system enabled by the flexible wall., Comment: 8 pages

Active matter exhibits striking behaviour reminiscent of living matter and molecular fluids, and has promising applications in drug delivery or mixing at the micron scale. Active colloidal systems provide important models with simple and controllable interactions amenable to theory and computer simulation. Experimental work is dominated by (quasi) two--dimensional (2d) systems at relatively low concentration, and rather less is known of the 3d case at concentrations pertinent to motility induced phase separation or to mimic morphogenesis. Here we investigate a 3d experimental system of active colloids in a dense suspension up to volume fractions of 0.5. The particles in our system are self-propelled in the lateral plane under an AC electric field. The field in addition induces an electric dipole, and the competition between activity and both steric and dipolar interactions gives rise to phase behaviour ranging from an active gas to a dynamic labyrinthine phase as well as dense tetragonal and hexagonal crystals. Intermediate volume fractions are characterised by two--dimensional sheets with large fluctuations reminiscent of active membranes. These active sheets break symmetry in a direction perpendicular to the applied field. Moreover, the relationship between electric field and the particle dynamics depends in a complex and unexpected manner upon the position in the state diagram.

In the COVID--19 pandemic, among the more controversial issues is the use of masks and face coverings. Much of the concern boils down to the question -- just how effective are face coverings? One means to address this question is to review our understanding of the physical mechanisms by which masks and coverings operate -- steric interception, inertial impaction, diffusion and electrostatic capture. We enquire as to what extent these can be used to predict the efficacy of coverings. We combine the predictions of the models of these mechanisms which exist in the filtration literature and compare the predictions with recent experiments and lattice Boltzmann simulations, and find reasonable agreement with the former and good agreement with the latter. Building on these results, we explore the parameter space for woven cotton fabrics to show that three-layered cloth masks can be constructed with comparable filtration performance to surgical masks under ideal conditions. Reusable cloth masks thus present an environmentally friendly alternative to surgical masks so long as the face seal is adequate enough to minimise leakage., Comment: 26 pages (13 + references, 10 pages supplementary), 10 figures (8 in main text, 2 in SI); accepted version, to appear in Physics of Fluids' special issue "Flow and the Virus"

We use a mixture of a polymer and its dimer to control dynamics in a manner inspired by \emph{pinning} a fraction of the system. In our system of $\alpha$-methyl styrene, where the polymer has a glass transition at higher temperature than the dimer, at intermediate temperatures, the polymer acts to "pin" the dimer. Within this temperature range, we use differential scanning calorimetry to infer a point-to-set length which we find to be profoundly influenced by the degree of pinning. We determine the dynamics of the system with dielectric spectroscopy and find that while the dynamics are very substantially slowed by the "pinning", the fragility exhibits only a small change relative to the precision of our measurements. This may indicate that in the approach we have used, fragility has a relatively weak dependence on quantities such as the point--to--set length. % than one might expect, However, an alternative explanation is that the dimer may act to \emph{plasticize} the polymer and thus open routes to relaxation that may be inaccessible to fully pinned systems., Comment: 18 pages, 4 figures

We review recent developments in structural-dynamical phase transitions in trajectory space. An open question is how the dynamic facilitation theory of the glass transition may be reconciled with thermodynamic theories that posit a vanishing configurational entropy. Dynamic facilitation theory invokes a dynamical phase transition, between an active phase (close to the normal liquid) and an inactive phase which is glassy, whose order parameter is either dynamic or a time-averaged structural quantity. In particular, the dynamical phase transition in systems with non-trivial thermodynamics manifests signatures of a lower critical point, which lies close to the putative Kauzmann temperature, where any thermodynamic phase transition to an ideal glass state might occur. We discuss these findings, and suggest that the lower critical point of the structural-dynamical phase transition may be related to the large drop in configurational entropy that occurs in the inactive phase of the dynamical phase transition. Increasing supercooling thus brings configurational entropy of the normal liquid much lower, along with the temperature., Comment: accepted in J. Chem. Phys

A quantitative understanding of the evaporative drying kinetics and nucleation rates of aqueous based aerosol droplets is important for a wide range of applications, from atmospheric aerosols to industrial processes such as spray drying. Here, we introduce a numerical model for interpreting measurements of the evaporation rate and phase change of drying free droplets made using a single particle approach. We explore the evaporation of aqueous sodium chloride and sodium nitrate solution droplets. Although the chloride salt is observed to reproducibly crystallise at all drying rates, the nitrate salt solution can lose virtually all of its water content without crystallising. The latter phenomenon has implications for our understanding of the competition between the drying rate and nucleation kinetics in these two systems. The nucleation model is used in combination with the measurements of crystallisation events to infer nucleation rates at varying equilibrium state points, showing that classical nucleation theory provides a good description of the crystallisation of the chloride salt but not the nitrate salt solution droplets. The reasons for this difference are considered., Comment: 10 pages, 7 figures

Colloidal suspensions have long been studied as a model for atomic and molecular systems, due to the ability to fluorescently label and individually track each particle, yielding particle-resolved structural information. This allows various local order parameters to be probed that are otherwise inaccessible for a comparable molecular system. For phase transitions such as crystallisation, appropriate order parameters which emphasise 6-fold symmetry are a natural choice, but for vitrification the choice of order parameter is less clear cut. Previous work has highlighted the importance of icosahedral local structure as the glass transition is approached. However, counting icosahedra or related motifs is not a continuous order parameter in the same way as, for example, the bond-orientational order parameters $Q_{6}$ and $W_6$. In this work we investigate the suitability of using pentagonal bipyramid membership, a structure which can be assembled into larger, five-fold symmetric structures, as a finer order parameter to investigate the glass transition. We explore various structural and dynamic properties and show that this new approach produces many of the same findings as simple icosahedral membership, but we also find that large instantaneous displacements are often correlated with significant changes in pentagonal bipyramid membership, and unlike the population of defective icosahedra, the pentagonal bypyramid membership and spindle number do not saturate for any measured volume fraction, but continues to increase., Comment: accepted by JStat Mech: Theory and Experiment 2019

The morphometric approach is a powerful ansatz for decomposing the chemical potential for a complex solute into purely geometrical terms. This method has proven accuracy in hard spheres, presenting an alternative to comparatively expensive (classical) density functional theory approaches. Despite this, fundamental questions remain over why it is accurate and how one might include higher-order terms to improve accuracy. We derive the morphometric approach as the exact resummation of terms in the virial series, providing further justification of the approach. The resulting theory is less accurate than previous morphometric theories, but provides fundamental insights into the inclusion of higher-order terms and to extensions to mixtures of convex bodies of arbitrary shape., Comment: 10 pages, 2 figures

Swimmers and self-propelled particles are physical models for the collective behaviour and motility of a wide variety of living systems, such as bacteria colonies, bird flocks and fish schools. Such artificial active materials are amenable to physical models which reveal the microscopic mechanisms underlying the collective behaviour. Here we study colloids in a DC electric field. Our quasi-two-dimensional system of electrically-driven particles exhibits a rich and exotic phase behaviour. At low field strengths, electrohydrodynamic flows lead to self-organisation into crystallites with hexagonal order. Upon self-propulsion of the particles due to Quincke rotation, we find an ordered phase of active matter in which the motile crystallites constantly change shape and collide with one another. At higher field strengths, this "dissolves" to an active gas. We parameterise a particulate simulation model which reproduces the experimentally observed phases and, at higher field strengths predicts an activity-driven demixing to band-like structures.

The discrepancy in nucleation rate densities between simulated and experimental hard spheres remains staggering and unexplained. Suggestively, more strongly sedimenting colloidal suspensions of hard spheres nucleate much faster than weakly sedimenting systems. In this work we consider firstly the effect of sedimentation on the structure of colloidal hard spheres, by tuning the density mismatch between solvent and colloidal particles. In particular we investigate the effect on the degree of five fold symmetry present. Secondly we study the size of density fluctuations in these experimental systems in comparison to simulations. The density fluctuations are measured by assigning each particle a local density, which is related to the number of particles within a distance of 3.25 particle diameters. The standard deviation of these local densities gives an indication of the fluctuations present in the system. Five fold symmetry is suppressed by a factor of two when sedimentation is induced in our system. Density fluctuations are also increased by a factor of two in experiments compared to simulations. The change in five fold symmetry makes a difference to the expected nucleation rates, but we demonstrate that it is ultimately too small to resolve the discrepancy between experiment and simulation, while the fluctuations are shown to be an artefact of 3d particle tracking., Comment: 8 pages

Using computer simulations, we study the dynamic arrest in a schematic model of colloid-polymer mixtures combining short-ranged attractions with long-ranged repulsions. The arrested gel is a dilute rigid network of colloidal particles bonded due to the strong attractions. Without repulsions, the gel forms at the spinodal through arrested phase separation. In the ergodic suspension at sufficiently high densities, colloidal clusters form temporary networks that percolate space. Recently [Nat. Commun. 7, 11817 (2016)], it has been proposed that the transition of these networks to directed percolation coincides with the onset of the dynamic arrest, thus linking structure to dynamics. Here, we evaluate for various screening lengths the underlying gas-liquid binodal and the percolation transitions. We find that directed percolation shifts the continuous percolation line to larger densities, but even beyond this line the suspension remains ergodic. Only when approaching the spinodal does dynamic arrest occur. Competing repulsions thus do not modify the qualitative scenario for non-equilibrium gelation, although the structure of the emerging percolating network shows some differences.

Spinodal demixing of systems into two phases having very different viscosities leads to viscoelastic networks, i.e. gels. Here we consider demixing in a colloidal system where one phase is a nematic liquid crystal with a strongly anisotropic viscosity. We combine real space analysis of a sepiolite clay system with molecular dynamics computer simulation. We find a long-lived network with many of the characteristics of a colloidal gel. Remarkably the anisotropic viscosity means that flow is possible within the nematic network, but only along the network, which thus preserves its structure, leading to a new form of anisotropic gel. Our system presents a further novel property, in that it is comprised of hard particles. Thus our dynamically anisotropic gels form in the absence of attraction between the particles. Thus we show that our new system exhibits the ingredients of gelation and conclude that it represent a new class of material, \emph{non-sticky} gels in which attractions are not present., Comment: 10 pages

Liquids in systems with spherically symmetric interactions are not thermodynamically stable when the range of the attraction is reduced sufficiently. However, these metastable liquids have lifetimes long enough that they are readily observable prior to crystallisation. Here we investigate the fate of liquids when the interaction range is reduced dramatically. Under these conditions, we propose that the liquid becomes kinetically unstable, i.e. its properties are non-stationary on the timescale of structural relaxation. Using molecular dynamics simulations, we find that in the square well model with range 6% of the diameter, the liquid crystallises within the timescale of structural relaxation for state points except those so close to criticality that the lengthscale of density fluctuations couples to the length of the simulation box size for typical system sizes. Even very close to criticality, the liquid exhibits significant structural change on the timescale of relaxation., Comment: 8 pages, accepted in special issue of Molecular Physics in honour of Daan Frenkel

In macroscopic mechanical devices torque is transmitted through gearwheels and clutches. In the construction of devices at the nanoscale, torque and its transmission through soft materials will be a key component. However, this regime is dominated by thermal fluctuations leading to dissipation. Here we demonstrate the principle of torque transmission for a disc-like colloidal assembly exhibiting clutch-like behaviour, driven by $27$ particles in optical traps. These are translated on a circular path to form a rotating boundary that transmits torque to additional particles confined to the interior. We investigate this transmission and find that it is determined by solid-like or fluid-like behaviour of the device and a stick-slip mechanism reminiscent of macroscopic gearwheels slipping. The transmission behaviour is predominantly governed by the rotation rate of the boundary and the density of the confined system. We determine the efficiency of our device and thus optimise conditions to maximise power output., Comment: 12 pages

We review efforts to realise so-called mermaid (or short-ranged attraction/long ranged repulsion) interactions in 3d real space. The repulsive and attractive contributions to these interactions in charged colloids and colloid-polymer mixtures, may be accurately realised, by comparing particle-resolved studies with colloids to computer simulation. However, when we review work where these interactions have been combined, despite early indications of behaviour consistent with predictions, closer analysis reveals that in the non-aqueous systems used for particle-resolved studies, the idea of summing the attractive and repulsive components leads to wild deviations with experiment. We suggest that the origin lies in the weak ion dissociation in these systems with low dielectric constant solvents. Ultimately this leads even to non-centro-symmetric interactions and a new level of complexity in these systems., Comment: 10 pages, accepted in Soft Matter

We propose a novel microfluidic "opposed-flow" geometry in which the continuous fluid phase is fed into a junction in a direction opposite the dispersed phase. This pulls out the dispersed phase into a micron-sized jet, which decays into micron-sized droplets. As the driving pressure is tuned to a critical value, the jet radius vanishes as a power law down to sizes below 1 $\mu$m. By contrast, the conventional "coflowing" junction leads to a first order jetting transition, in which the jet disappears at a finite radius of several $\mu$m, to give way to a "dripping" state, resulting in much larger droplets. We demonstrate the effectiveness of our method by producing the first microfluidic silicone oil emulsions with a sub micron particle radius, and utilize these droplets to produce colloidal clusters.

Crucial to gaining control over crystallisation in multicomponent materials or accurately modelling rheological behaviour of magma flows is to understand the mechanisms by which crystal nuclei form. The microscopic nature of such nuclei, however, makes this extremely hard in experiments, while computer simulations have hitherto been hampered by their short timescales and small system sizes due to limited computational power. Here we use highly-efficient GPU simulation techniques to access system sizes around 100 times larger than previous studies. This makes it possible to elucidate the nucleation mechanism in a well-studied binary glassformer. We discover that the supercooled liquid is inherently unstable for system sizes of 10,000 particles and larger. This effect is due to compositional fluctuations leading to regions comprised of large particles only which rapidly nucleate. We argue that this mechanism provides a minimum rate of crystallisation in mixtures in general, and use our results to stabilise a model binary mixture and predict glassforming ability for the CuZr metallic glassformer., Comment: 11 pages

In trajectory space, dynamical heterogeneities in glass-forming liquids correspond to the emergence of a dynamical phase transition between an active phase poor in local structure and an inactive phase which is rich in local structure. We support this scenario with the study of a model additive mixture of Lennard-Jones particles, quantifying how the choice of the relevant structural and dynamical observable affects the transition in trajectory space. We find that the low mobility, structure-rich phase is dominated by icosahedral order. Applying a nonequilibrium rheological protocol, we connect local order to the emergence of mechanical rigidity.

We consider the yielding under simple shear of a binary Lennard-Jones glassformer whose super-Arrhenius dynamics are correlated with the formation of icosahedral structures. We recast this glassformer as an effective system of icosahedra [Pinney et al. J. Chem. Phys. 143 244507 (2015)]. Looking at the small-strain region of sheared simulations, we observe that shear rates affect the shear localisation behavior particularly at temperatures below the glass transition as defined with a fit to the Vogel-Fulcher-Tamman equation. At higher temperature, shear localisation starts immediately upon shearing for all shear rates. At lower temperatures, faster shear rates can result in a delayed start in shear localisation; which begins close to the yield stress. Building from a previous work which considered steady-state shear [Pinney et al. J. Chem. Phys. 143 244507 (2016)], we interpret the response to shear and the shear localisation in terms of a \emph{local} effective temperature with our system of icosahedra. We find that the effective temperatures of the regions undergoing shear localisation increase significantly with increasing strain (before reaching a steady state plateau)., Comment: 13 pages, accepted in Phys. Rev. E

A quasi two-dimensional colloidal suspension is studied under the influence of immobilisation (pinning) of a random fraction of its particles. We introduce a novel experimental method to perform random pinning and, with the support of numerical simulation, we find that increasing the pinning concentration smoothly arrests the system, with a cross-over from a regime of high mobility and high entropy to a regime of low mobility and low entropy. At the local level, we study fluctuations in area fraction and concentration of pins and map them to entropic structural signatures and local mobility, obtaining a measure for the local entropic fluctuations of the experimental system.

We combine experiments and simulations to study the link between criticality and gelation in sticky spheres. We employ confocal microscopy to image colloid-polymer mixtures, and Monte Carlo simulations of the square-well (SW) potential as a reference model. To this end, we map our experimental samples onto the SW model. We find excellent structural agreement between experiments and simulations, both for locally favored structures at the single particle level and large-scale fluctuations at criticality. We follow in detail the rapid structural change of the critical fluid when approaching the gas-liquid binodal and highlight the role of critical density fluctuations for this structural crossover. Our results link the arrested spinodal decomposition to long-lived energetically favored structures, which grow even away from the binodal due to the critical scaling of the bulk correlation length and static susceptibility.

Understanding the phase behaviour of mixtures continues to pose challenges, even for systems that might be considered "simple". Here we consider a very simple mixture of two colloidal and one non-adsorbing polymer species which can be simplified even further to a size-asymmetrical binary mixture, in which the effective colloid-colloid interactions depend on the polymer concentration. We show that this basic system exhibits surprisingly rich phase behaviour. In particular, we enquire whether such a system features only a liquid-vapor phase separation (as in one-component colloid-polymer mixtures) or whether, additionally, liquid-liquid demixing of two colloidal phases can occur. Particle-resolved experiments show demixing-like behaviour, but when combined with bespoke Monte Carlo simulations, this proves illusory, and we reveal that only a single liquid-vapor transition occurs. Progressive migration of the small particles to the liquid phase as the polymer concentration increases gives rise to composition inversion - a maximum in the large particle concentration in the liquid phase. Near criticality the density fluctuations are found to be dominated by the larger colloids., Comment: submitted to J. Chem. Phys

Key to resolving the scientific challenge of the glass transition is to understand the origin of the massive increase in viscosity of liquids cooled below their melting temperature (avoiding crystallisation). A number of competing and often mutually exclusive theoretical approaches have been advanced to describe this phenomenon. Some posit a bona fide thermodynamic phase to an "ideal glass", an amorphous state with exceptionally low entropy. Other approaches are built around the concept of the glass transition as a primarily dynamic phenomenon. These fundamentally different interpretations give equally good descriptions of the data available, so it is hard to determine which -- if any -- is correct. Recently however this situation has begun to change. A consensus has emerged that one powerful means to resolve this longstanding question is to approach the putative thermodynamic transition sufficiently closely, and a number of techniques have emerged to meet this challenge. Here we review the results of some of these new techniques and discuss the implications for the existence -- or otherwise -- of the thermodynamic transition to an ideal glass., Comment: 42 pages

We consider a binary Lennard-Jones glassformer whose super-Arrhenius dynamics are correlated with the formation of particles organized into icosahedra under simple steady state shear. We recast this glassformer as an effective system of icosahedra [Pinney et al. J. Chem. Phys. 143 244507 (2015)]. From the observed population of icosahedra in each steady state, we obtain an effective temperature which is linearly dependent on the shear rate in the range considered. Upon shear banding, the system separates into a region of high shear rate and a region of low shear rate. The effective temperatures obtained in each case show that the low shear regions correspond to a significantly lower temperature than the high shear regions. Taking a weighted average of the effective temperature of these regions (weight determined by region size) yields an estimate of the effective temperature which compares well with an effective temperature based on the global mesocluster population of the whole system., Comment: accepted by J. Chehm. Phys

We investigate the static and dynamic properties of a weakly polydisperse hard sphere system in the deeply supercooled state, i.e. at densities higher than that corresponding to the mode-coupling transition. The structural analysis reveals the emergence of icosahedral locally favoured structures, previously only found in trace quantities. We present a new approach to probe the shape of dynamically heterogeneous regions, which is insensitive to particle packing effects that can hamper such analysis. Our results indicate that the shape of the dynamically heterogeneous regions changes only weakly and moreover hint that the often-used four-point correlation length may exhibit a growth in excess of that which our method identifies. The growth of the size of the dynamically heterogeneous regions appears instead to be in line with the one of structural and dynamic propensity correlations., Comment: under review at J. Stat Mech: Theory and Experiment

We consider the sedimentation of a colloidal gel under confinement in the direction of gravity. The confinement allows us to compare directly experiments and computer simulations, for the same system size in the vertical direction. The confinement also leads to qualitatively different behaviour compared to bulk systems: in large systems gelation suppresses sedimentation, but for small systems sedimentation is enhanced relative to non-gelling suspensions, although the rate of sedimentation is reduced when the strength of the attraction between the colloids is strong. We map interaction parameters between a model experimental system (observed in real space) and computer simulations. Remarkably, we find that when simulating the system using Brownian dynamics in which hydrodynamic interactions between the particles are neglected, we find that sedimentation occurs on the same timescale as the experiments, however the thickness of the "arms" of the gel is rather larger in the experiments, compared with the simulations. An analysis of local structure in the simulations showed similar behaviour to gelation in the absence of gravity.