Microscopic theory for nonequilibrium correlation functions in dense active fluids.

One of the key hallmarks of dense active matter in the liquid, supercooled, and solid phases is the so-called equal-time velocity correlations. Crucially, these correlations can emerge spontaneously, i.e., they require no explicit alignment interactions, and therefore represent a generic feature of dense active matter. This indicates that for a meaningful comparison or possible mapping between active and passive liquids one not only needs to understand their structural properties, but also the impact of these velocity correlations. This has already prompted several simulation and theoretical studies, though they are mostly focused on athermal systems and thus overlook the effect of translational diffusion. Here, we present a fully microscopic method to calculate nonequilibrium correlations in two-dimensional systems of thermal active Brownian particles (ABPs). We use the integration through transients formalism together with (active) mode-coupling theory and analytically calculate qualitatively consistent static structure factors and active velocity correlations. We complement our theoretical results with simulations of both thermal and athermal ABPs which exemplify the disruptive role that thermal noise has on velocity correlations.

Mode-coupling theory for mixtures of athermal self-propelled particles.

Dense or glassy active matter, as a result of its remarkable resemblance to passive glass-forming materials, is enjoying increasing scientific interest. To better grasp the subtle effect of active motion on the process of vitrification, a number of active mode-coupling theories (MCTs) have recently been developed. These have proven capable of qualitatively predicting important parts of the active glassy phenomenology. However, most efforts so far have only considered single-component materials, and their derivations are arguably more complex than the standard MCT case, which might hinder broader usage. Here we present a detailed derivation of a distinct active MCT for mixtures of athermal self-propelled particles that is more transparent than previously introduced versions. The key insight is that we can follow a similar strategy for our overdamped active system as is typically used for passive underdamped MCT. Interestingly, when only considering one particle species, our theory gives the exact same result as the one obtained in previous work, which employed a highly different mode-coupling strategy. Moreover, we assess the quality of the theory and its novel extension to multi-component materials by using it to predict the dynamics of a Kob-Andersen mixture of athermal active Brownian quasi-hard spheres. We demonstrate that our theory is able to capture all qualitative features, most notably the location of the optimum of the dynamics when the persistence length and cage length coincide, for each combination of particle types.

Emergent structural correlations in dense liquids.

The complete quantitative description of the structure of dense and supercooled liquids remains a notoriously difficult problem in statistical physics. Most studies to date focus solely on two-body structural correlations, and only a handful of papers have sought to consider additional three-body correlations. Here, we go beyond the state of the art by extracting many-body static structure factors from molecular dynamics simulations and by deriving accurate approximations up to the six-body structure factor via density functional theory. We find that supercooling manifestly increases four-body correlations, akin to the two- and three-body case. However, at small wave numbers, we observe that the four-point structure of a liquid drastically changes upon supercooling, both qualitatively and quantitatively, which is not the case in two-point structural correlations. This indicates that theories of the structure or dynamics of dense liquids should incorporate many-body correlations beyond the two-particle level to fully capture their intricate behavior.

A deep learning approach to the measurement of long-lived memory kernels from generalized Langevin dynamics.

Memory effects are ubiquitous in a wide variety of complex physical phenomena, ranging from glassy dynamics and metamaterials to climate models. The Generalized Langevin Equation (GLE) provides a rigorous way to describe memory effects via the so-called memory kernel in an integro-differential equation. However, the memory kernel is often unknown, and accurately predicting or measuring it via, e.g., a numerical inverse Laplace transform remains a herculean task. Here, we describe a novel method using deep neural networks (DNNs) to measure memory kernels from dynamical data. As a proof-of-principle, we focus on the notoriously long-lived memory effects of glass-forming systems, which have proved a major challenge to existing methods. In particular, we learn the operator mapping dynamics to memory kernels from a training set generated with the Mode-Coupling Theory (MCT) of hard spheres. Our DNNs are remarkably robust against noise, in contrast to conventional techniques. Furthermore, we demonstrate that a network trained on data generated from analytic theory (hard-sphere MCT) generalizes well to data from simulations of a different system (Brownian Weeks-Chandler-Andersen particles). Finally, we train a network on a set of phenomenological kernels and demonstrate its effectiveness in generalizing to both unseen phenomenological examples and supercooled hard-sphere MCT data. We provide a general pipeline, KernelLearner, for training networks to extract memory kernels from any non-Markovian system described by a GLE. The success of our DNN method applied to noisy glassy systems suggests that deep learning can play an important role in the study of dynamical systems with memory.

Steering self-organisation through confinement.

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 is an action over a system that limits its units' translational and rotational degrees of freedom, thus also influencing the system's phase space probability density; it can function as either a catalyst or inhibitor of self-organisation. Confinement 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 and perspective for future research, we examine the role of confinement in the self-organisation of soft-matter systems and identify overarching scientific challenges that need to be addressed to harness its full scientific and technological potential in soft matter and related fields. By drawing analogies with other disciplines, this framework will accelerate a common deeper understanding of self-organisation and trigger the development of innovative strategies to steer it using confinement, with impact on, e.g., the design of smarter materials, tissue engineering for biomedicine and in guiding active matter.

Glassy Dynamics in Chiral Fluids.

Chiral active matter is enjoying a rapid increase of interest, spurred by the rich variety of asymmetries that can be attained in, e.g., the shape or self-propulsion mechanism of active particles. Though this has already led to the observance of so-called chiral crystals, active chiral glasses remain largely unexplored. A possible reason for this could be the naive expectation that interactions dominate the glassy dynamics and the details of the active motion become increasingly less relevant. Here, we show that quite the opposite is true by studying the glassy dynamics of interacting chiral active Brownian particles. We demonstrate that when our chiral fluid is pushed to glassy conditions, it exhibits highly nontrivial dynamics, especially compared to a standard linear active fluid such as common active Brownian particles. Despite the added complexity, we are still able to present a full rationalization for all identified dynamical regimes. Most notably, we introduce a new "hammering" mechanism, unique to rapidly spinning particles in high-density conditions, that can fluidize a chiral active solid.

Acoustic Crystallization of 2D Colloidal Crystals.

2D colloidal crystallization provides a simple strategy to produce defined nanostructure arrays over macroscopic areas. Regularity and long-range order of such crystals is essential to ensure functionality, but difficult to achieve in self-assembling systems. Here, a simple loudspeaker setup for the acoustic crystallization of 2D colloidal crystals (ACDC) of polystyrene, microgels, and core-shell particles at liquid interfaces is introduced. This setup anneals an interfacial colloidal monolayer and affords an increase in average grain size by almost two orders of magnitude. The order is characterized via the structural color of the colloidal crystal, the acoustic annealing process is optimized via the frequency and the amplitude of the applied sound wave, and its efficiency is rationalized via the surface coverage-dependent interactions within the interfacial colloidal monolayer. Computer simulations show that multiple rearrangement mechanisms at different length scales, from the local motion around voids to grain boundary movements via consecutive particle rotations around common centers, collude to remove defects. The experimentally simple ACDC process, paired with the demonstrated applicability toward complex particle systems, provides access to highly defined nanostructure arrays for a wide range of research communities.

Active glassy dynamics is unaffected by the microscopic details of self-propulsion.

Recent years have seen a rapid increase of interest in dense active materials, which, in the disordered state, share striking similarities with the conventional passive glass-forming matter. For such passive glassy materials, it is well established (at least in three dimensions) that the details of the microscopic dynamics, e.g., Newtonian or Brownian, do not influence the long-time glassy behavior. Here, we investigate whether this still holds true in the non-equilibrium active case by considering two simple and widely used active particle models, i.e., active Ornstein-Uhlenbeck particles (AOUPs) and active Brownian particles (ABPs). In particular, we seek to gain more insight into the role of the self-propulsion mechanism on the glassy dynamics by deriving a mode-coupling theory (MCT) for thermal AOUPs, which can be directly compared to a recently developed MCT for ABPs. Both theories explicitly take into account the active degrees of freedom. We solve the AOUP- and ABP-MCT equations in two dimensions and demonstrate that both models give almost identical results for the intermediate scattering function over a large variety of control parameters (packing fractions, active speeds, and persistence times). We also confirm this theoretical equivalence between the different self-propulsion mechanisms numerically via simulations of a polydisperse mixture of active quasi-hard spheres, thereby establishing that, at least for these model systems, the microscopic details of self-propulsion do not alter the active glassy behavior.

Many-Body Correlations Are Non-negligible in Both Fragile and Strong Glassformers.

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 nontrivial competition between static triplet correlations that work to stabilize the glass state and dynamic higher-order correlations that 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.

Dynamical susceptibilities near ideal glass transitions.

Building on the recently derived inhomogeneous mode-coupling theory, we extend the generalized mode-coupling theory of supercooled liquids to inhomogeneous environments. This provides a first-principles-based, systematic, and rigorous way of deriving high-point dynamical susceptibilities from variations of the many-body dynamic structure factors with respect to their conjugate field. This framework allows for a fully microscopic possibility to probe for collective relaxation mechanisms in supercooled liquids near the mode-coupling glass transition. The behavior of these dynamical susceptibilities is then studied in the context of simplified self-consistent relaxation models.

Glassy dynamics of sticky hard spheres beyond the mode-coupling regime.

Sticky hard spheres, i.e., hard particles decorated with a short-ranged attractive interaction potential, constitute a relatively simple model with highly non-trivial glassy dynamics. The mode-coupling theory of the glass transition (MCT) offers a qualitative account of the complex reentrant dynamics of sticky hard spheres, but the predicted glass transition point is notoriously underestimated. Here we apply an improved first-principles-based theory, referred to as generalized mode-coupling theory (GMCT), to sticky hard spheres. This theoretical framework seeks to go beyond MCT by hierarchically expanding the dynamics in higher-order density correlation functions. We predict the phase diagrams from the first few levels of the GMCT hierarchy and the dynamics-related critical exponents, all of which are much closer to the empirical observations than MCT. Notably, the prominent reentrant glassy dynamics, the glass-glass transition, and the higher-order bifurcation singularity classes (A3 and A4) of sticky hard spheres are found to be preserved within GMCT at arbitrary order. Moreover, we demonstrate that when the hierarchical order of GMCT increases, the effect of the short-ranged attractive interactions becomes more evident in the dynamics. This implies that GMCT is more sensitive to subtle microstructural differences than MCT, and that the framework provides a promising first-principles approach to systematically go beyond the MCT regime.

Tagged-particle motion of Percus-Yevick hard spheres from first principles.

We develop a first-principles-based generalized mode-coupling theory (GMCT) for the tagged-particle motion of glassy systems. This theory establishes a hierarchy of coupled integro-differential equations for self-multi-point density correlation functions, which can formally be extended up to infinite order. We use our GMCT framework to calculate the self-nonergodicity parameters and the self-intermediate scattering function for the Percus-Yevick hard-sphere system based on the first few levels of the GMCT hierarchy. We also test the scaling laws in the α- and ß-relaxation regimes near the glass-transition singularity. Furthermore, we study the mean-square displacement and the Stokes-Einstein relation in the supercooled regime. We find that qualitatively our GMCT results share many similarities with the well-established predictions from standard mode-coupling theory, but the quantitative results change, and typically improve, by increasing the GMCT closure level. However, we also demonstrate on general theoretical grounds that the current GMCT framework is unable to account for violation of the Stokes-Einstein relation, underlining the need for further improvements in the first-principles description of glassy dynamics.

Multi-component generalized mode-coupling theory: predicting dynamics from structure in glassy mixtures.

The emergence of glassy dynamics and the glass transition in dense disordered systems is still not fully understood theoretically. Mode-coupling theory (MCT) has shown to be effective in describing some of the non-trivial features of glass formation, but it cannot explain the full glassy phenomenology due to the strong approximations on which it is based. Generalized mode-coupling theory (GMCT) is a hierarchical extension of the theory, which is able to outclass MCT by carefully describing the dynamics of higher-order correlations in its generalized framework. Unfortunately, the theory has so far only been developed for single-component systems and as a result works poorly for highly polydisperse materials. In this paper, we solve this problem by developing GMCT for multi-component systems. We use it to predict the glassy dynamics of the binary Kob-Andersen Lennard-Jones mixture, as well as its purely repulsive Weeks-Chandler-Andersen analogue. Our results show that each additional level of the GMCT hierarchy gradually improves the predictive power of GMCT beyond its previous limit. This implies that our theory is able to harvest more information from the static correlations, thus being able to better understand the role of attraction in supercooled liquids from a first-principles perspective.

Collapse-induced phase transitions in binary interfacial microgel monolayers.

Microgels, consisting of a swollen polymer network, exhibit a more complex self-assembly behavior compared to incompressible colloidal particles, because of their ability to deform at a liquid interface or collapse upon compression. Here, we investigate the collective phase behavior of two-dimensional binary mixtures of microgels confined at the air/water interface. We use stimuli-responsive poly(N-isopropylacrylamide) microgels with different crosslinking densities, and therefore different morphologies at the interface. We find that the minority microgel population introduces lattice defects in the ordered phase of the majority population, which, in contrast to bulk studies, do not heal out by partial deswelling to accommodate in the lattice. We subsequently investigate the interfacial phase behavior of these binary interfacial assemblies under compression. The binary system exhibits three distinct isostructural solid-solid phase transitions, during which the coronae between two small particles collapse first, followed by the collapse between small-large and large-large microgel pairs. A similar hierarchy of phase transitions is found for mixtures of microgels and core-shell particles. Simulations based on augmented potentials qualitatively reproduce the experimentally observed phase transitions. We rationalize the presence of this hierarchy in phase transitions from differences in the interfacial morphology between the species: the larger coronae of softer (and therefore larger) microgels provide a higher resistance to phase transitions compared to the smaller coronae of the more crosslinked microgels and core-shell particles. The control of phase transitions via the molecular architecture further allows the formation of characteristic, flower-like defects by introducing particles with "weaker" coronae that are more prone to collapse with their neighboring particles. Our findings underline the dominating role of the corona for interfacial microgel assemblies, which acts as an energy barrier, shifting the collapse to higher surface pressures.

Interface-induced hysteretic volume phase transition of microgels: simulation and experiment.

Thermo-responsive microgel particles can exhibit a drastic volume shrinkage upon increasing the solvent temperature. Recently we found that the spreading of poly(N-isopropylacrylamide) (PNiPAm) microgels at a liquid interface under the influence of surface tension hinders the temperature-induced volume phase transition. In addition, we observed a hysteresis behavior upon temperature cycling, i.e. a different evolution in microgel size and shape depending on whether the microgel was initially adsorbed to the interface in expanded or collapsed state. Here, we model the volume phase transition of such microgels at an air/water interface by monomer-resolved Brownian dynamics simulations and compare the observed behavior with experiments. We reproduce the experimentally observed hysteresis in the microgel dimensions upon temperature variation. Our simulations did not observe any hysteresis for microgels dispersed in the bulk liquid, suggesting that it results from the distinct interfacial morphology of the microgel adsorbed at the liquid interface. An initially collapsed microgel brought to the interface and subjected to subsequent swelling and collapsing (resp. cooling and heating) will end up in a larger size than it had in the original collapsed state. Further temperature cycling, however, only shows a much reduced hysteresis, in agreement with our experimental observations. We attribute the hysteretic behavior to a kinetically trapped initial collapsed configuration, which relaxes upon expanding in the swollen state. We find a similar behavior for linear PNiPAm chains adsorbed to an interface. Our combined experimental - simulation investigation provides new insights into the volume phase transition of PNiPAm materials adsorbed to liquid interfaces.

Soft Particles at Liquid Interfaces: From Molecular Particle Architecture to Collective Phase Behavior.

Soft particles such as microgels can undergo significant and anisotropic deformations when adsorbed to a liquid interface. This, in turn, leads to a complex phase behavior upon compression. To date, experimental efforts have predominantly provided phenomenological links between microgel structure and resulting interfacial behavior, while simulations have not been entirely successful in reproducing experiments or predicting the minimal requirements for the desired phase behavior. Here, we develop a multiscale framework to link the molecular particle architecture to the resulting interfacial morphology and, ultimately, to the collective interfacial phase behavior. To this end, we investigate interfacial morphologies of different poly(N-isopropylacrylamide) particle systems using phase-contrast atomic force microscopy and correlate the distinct interfacial morphology with their bulk molecular architecture. We subsequently introduce a new coarse-grained simulation method that uses augmented potentials to translate this interfacial morphology into the resulting phase behavior upon compression. The main novelty of this method is the possibility to efficiently encode multibody interactions, the effects of which are key to distinguishing between heterostructural (anisotropic collapse) and isostructural (isotropic collapse) phase transitions. Our approach allows us to qualitatively resolve existing discrepancies between experiments and simulations. Notably, we demonstrate the first in silico account of the two-dimensional isostructural transition, which is frequently found in experiments but elusive in simulations. In addition, we provide the first experimental demonstration of a heterostructural transition to a chain phase in a single-component system, which has been theoretically predicted decades ago. Overall, our multiscale framework provides a phenomenological bridge between physicochemical soft-particle characteristics at the molecular scale and nanoscale and the collective self-assembly phenomenology at the macroscale, serving as a stepping stone toward an ultimately more quantitative and predictive design approach.

Enhanced persistence and collective migration in cooperatively aligning cell clusters.

Most cells possess the capacity to locomote. Alone or collectively, this allows them to adapt, to rearrange, and to explore their surroundings. The biophysical characterization of such motile processes, in health and in disease, has so far focused mostly on two limiting cases: single-cell motility on the one hand and the dynamics of confluent tissues such as the epithelium on the other. The in-between regime of clusters, composed of relatively few cells moving as a coherent unit, has received less attention. Such small clusters are, however, deeply relevant in development but also in cancer metastasis. In this work, we use cellular Potts models and analytical active matter theory to understand how the motility of small cell clusters changes with N, the number of cells in the cluster. Modeling and theory reveal our two main findings: cluster persistence time increases with N, whereas the intrinsic diffusivity decreases with N. We discuss a number of settings in which the motile properties of more complex clusters can be analytically understood, revealing that the focusing effects of small-scale cooperation and cell-cell alignment can overcome the increased bulkiness and internal disorder of multicellular clusters to enhance overall migrational efficacy. We demonstrate this enhancement for small-cluster collective durotaxis, which is shown to proceed more effectively than for single cells. Our results may provide some novel, to our knowledge, insights into the connection between single-cell and large-scale collective motion and may point the way to the biophysical origins of the enhanced metastatic potential of small tumor cell clusters.

Cage Length Controls the Nonmonotonic Dynamics of Active Glassy Matter.

Dense active matter is gaining widespread interest due to its remarkable similarity with conventional glass-forming materials. However, active matter is inherently out of equilibrium and even simple models such as active Brownian particles (ABPs) and active Ornstein-Uhlenbeck particles (AOUPs) behave markedly differently from their passive counterparts. Controversially, this difference has been shown to manifest itself via either a speedup, slowdown, or nonmonotonic change of the glassy relaxation dynamics. Here we rationalize these seemingly contrasting views on the departure from equilibrium by identifying the ratio of the short-time length scale to the cage length, i.e., the length scale of local particle caging, as a vital and unifying control parameter for active glassy matter. In particular, we explore the glassy dynamics of both thermal and athermal ABPs and AOUPs upon increasing the persistence time. We find that for all studied systems there is an optimum of the dynamics; this optimum occurs when the cage length coincides with the corresponding short-time length scale of the system, which is either the persistence length for athermal systems or a combination of the persistence length and a diffusive length scale for thermal systems. This new insight, for which we also provide a simple physical argument, allows us to reconcile and explain the manifestly disparate departures from equilibrium reported in many previous studies of dense active materials.

Generalized mode-coupling theory for mixtures of Brownian particles.

Generalized mode-coupling theory (GMCT) has recently emerged as a promising first-principles theory to study the poorly understood dynamics of glass-forming materials. Formulated as a hierarchical extension of standard mode-coupling theory (MCT), it is able to systematically improve its predictions by including the exact dynamics of higher-order correlation functions into its hierarchy. However, in contrast to Newtonian dynamics, a fully generalized version of the theory based on Brownian dynamics is still lacking. To close this gap, we provide a detailed derivation of GMCT for colloidal mixtures obeying a many-body Smoluchowski equation. We demonstrate that a hierarchy of coupled equations can again be established and show that these, consistent with standard MCT, are identical to the ones obtained from Newtonian GMCT when taking the overdamped limit. Consequently, the nontrivial similarity between Brownian and Newtonian MCT is maintained for our multicomponent GMCT. As a proof of principle, we also solve the generalized mode-coupling equations for the binary Kob-Andersen Lennard-Jones mixture undergoing Brownian dynamics and confirm the improved predictive power of the theory upon using more levels of the GMCT hierarchy of equations.

Generalized mode-coupling theory of the glass transition. I. Numerical results for Percus-Yevick hard spheres.

Mode-coupling theory (MCT) constitutes one of the few first-principles-based approaches to describe the physics of the glass transition, but the theory's inherent approximations compromise its accuracy in the activated glassy regime. Here, we show that microscopic generalized mode-coupling theory (GMCT), a recently proposed hierarchical framework to systematically improve upon MCT, provides a promising pathway toward a more accurate first-principles description of glassy dynamics. We present a comprehensive numerical analysis for Percus-Yevick hard spheres by performing explicitly wavenumber- and time-dependent GMCT calculations up to sixth order. Specifically, we calculate the location of the critical point, the associated non-ergodicity parameters, and the time-dependent dynamics of the density correlators at both absolute and reduced packing fractions, and we test several universal scaling relations in the α- and ß-relaxation regimes. It is found that higher-order GMCT can successfully remedy some of MCT's pathologies, including an underestimation of the critical glass transition density and an overestimation of the hard-sphere fragility. Furthermore, we numerically demonstrate that the celebrated scaling laws of MCT are preserved in GMCT and that the predicted critical exponents manifestly improve as more levels are incorporated in the GMCT hierarchy. Although formally the GMCT equations should be solved up to infinite order to reach full convergence, our finite-order GMCT calculations unambiguously reveal a uniform convergence pattern for the dynamics. We thus argue that GMCT can provide a feasible and controlled means to bypass MCT's main uncontrolled approximation, offering hope for the future development of a quantitative first-principles theory of the glass transition.