Nonmonotonic Dynamical Correlations beneath the Surface of Glass-Forming Liquids.

Collective motion over increasing length scales is a signature of the vitrification process of liquids. We demonstrate how distinct static and dynamic length scales govern the dynamics of vitrifying films. In contrast to a monotonically growing static correlation length, the dynamical correlation length that measures the extent of surface-dynamics acceleration into the bulk displays a striking nonmonotonic temperature evolution that is robust also against changes in detailed interatomic interaction. This nonmonotonic change defines a crossover temperature T_{*} that is distinct from the critical temperature T_{c} of mode-coupling theory. We connect this nonmonotonic change to a morphological change of cooperative rearrangement regions of fast particles, and to the point where the decoupling of fast-particle motion from the bulk relaxation is most sensitive to fluctuations. We propose a rigorous definition of this new crossover temperature T_{*} within a recent extension of mode-coupling theory, the stochastic ß-relaxation theory.

From Subaging to Hyperaging in Structural Glasses.

We demonstrate nonequilibrium scaling laws for the aging and equilibration dynamics in glass formers that emerge from combining a relaxation equation for the static structure with the equilibrium scaling laws of glassy dynamics. Different scaling regimes are predicted for the evolution of the structural relaxation time τ with age (waiting time t_{w}), depending on the depth of the quench from the liquid into the glass: "simple" aging (τ∼t_{w}) applies for quenches close to the critical point of mode-coupling theory (MCT) and implies "subaging" (τ≈t_{w}^{δ} with δ<1) as a broad equilibration crossover for quenches to nearly arrested equilibrium states; "hyperaging" (or superaging, τ∼t_{w}^{δ^{'}} with δ^{'}>1) emerges for quenches deep into the glass. The latter is cut off by non-mean-field fluctuations that we account for within a recent extension of MCT, the stochastic ß-relaxation theory (SBR). We exemplify the scaling laws with a schematic model that quantitatively fits simulation data.

"Inner clocks" of glass-forming liquids.

Providing a physically sound explanation of aging phenomena in non-equilibrium amorphous materials is a challenging problem in modern statistical thermodynamics. The slow evolution of physical properties after quenches of control parameters is empirically well interpreted via the concept of material time (or internal clock) based on the Tool-Narayanaswamy-Moynihan model. Yet, the fundamental reasons of its striking success remain unclear. We propose a microscopic rationale behind the material time on the basis of the linear laws of irreversible thermodynamics and its extension that treats the corresponding kinetic coefficients as state functions of a slowly evolving material state. Our interpretation is based on the recognition that the same mathematical structure governs both the Tool model and the recently developed non-equilibrium extension of the self-consistent generalized Langevin equation theory, guided by the universal principles of Onsager's theory of irreversible processes. This identification opens the way for a generalization of the material-time concept to aging systems where several relaxation modes with very different equilibration processes must be considered, and partially frozen glasses manifest the appearance of partial ergodicity breaking and, hence, materials with multiple very distinct inner clocks.

Tracer dynamics in crowded active-particle suspensions.

We discuss the dynamics of active Brownian particles (ABPs) in crowded environments through the mean-squared displacement (MSD) of active and passive tracer particles in both active and passive host systems. Exact equations for the MSD are derived using a projection operator technique, extending to dense systems the known solution for a single ABP. The interaction of the tracer particle with the host particles gives rise to strong memory effects. Evaluating these approximately in the framework of a recently developed mode-coupling theory for active Brownian particles (ABP-MCT), we discuss the various dynamical regimes that emerge: While self-propelled motion gives rise to super-diffusive MSD, at high densities, this competes with an interaction-induced sub-diffusive regime. The predictions of the theory are shown to be in good agreement with results obtained from an event-driven Brownian dynamics (ED-BD) simulation scheme for the dynamics of two-dimensional active Brownian hard disks.

Transport coefficients in dense active Brownian particle systems: mode-coupling theory and simulation results.

We discuss recent advances in developing a mode-coupling theory of the glass transition (MCT) of two-dimensional systems of active Brownian particles (ABPs). The theory describes the structural relaxation close to the active glass in terms of transient dynamical density correlation functions. We summarize the equations of motion that have been derived for the collective density-fluctuation dynamics and those for the tagged-particle motion. The latter allow to study the dynamics of both passive and active tracers in both passive and active host systems. In the limit of small wave numbers, they give rise to equations of motion describing the mean-squared displacements (MSDs) of these tracers and hence the long-time diffusion coefficients as a transport coefficient quantifying long-range tracer motion. We specifically discuss the case of a single ABP tracer in a glass-forming passive host suspension, a case that has recently been studied in experiments on colloidal Janus particles. We employ event-driven Brownian dynamics (ED-BD) computer simulations to test the ABP-MCT and find good agreement between the two for the MSD, provided that known errors in MCT already for the passive system (i.e., an overestimation of the glassiness of the system) are accounted for by an empirical mapping of packing fractions and host-system self-propulsion forces. The ED-BD simulation results also compare well to experimental data, although a peculiar non-monotonic mapping of self-propulsion velocities is required. The ABP-MCT predicts a specific self-propulsion dependence of the Stokes-Einstein relation between the long-time diffusion coefficient and the host-system viscosity that matches well the results from simulation. An application of ABP-MCT within the integration-through transients framework to calculate the density-renormalized effective swim velocity of the interacting ABP agrees qualitatively with the ED-BD simulation data at densities close to the glass transition and quantitatively for the full density range only after the mapping of packing fractions employed for the passive system.

Solvable Models of Supercooled Liquids in Three Dimensions.

We introduce a supercooled liquid model and obtain parameter-free quantitative predictions that are in excellent agreement with numerical simulations, notably in the hard low-temperature region characterized by strong deviations from mode-coupling-theory behavior. The model is the Fredrickson-Andersen kinetically constrained model on the three-dimensional M-layer lattice. The agreement has implications beyond the specific model considered because the theory is potentially valid for many more systems, including realistic models and actual supercooled liquids.

Arrested dynamics of the dipolar hard sphere model.

We report the combined results of molecular dynamics simulations and theoretical calculations concerning various dynamical arrest transitions in a model system representing a dipolar fluid, namely, N (soft core) rigid spheres interacting through a truncated dipole-dipole potential. By exploring different regimes of concentration and temperature, we find three distinct scenarios for the slowing down of the dynamics of the translational and orientational degrees of freedom: at low (η = 0.2) and intermediate (η = 0.4) volume fractions, both dynamics are strongly coupled and become simultaneously arrested upon cooling. At high concentrations (η≥ 0.6), the translational dynamics shows the features of an ordinary glass transition, either by compressing or cooling down the system, but with the orientations remaining ergodic, thus indicating the existence of partially arrested states. In this density regime, but at lower temperatures, the relaxation of the orientational dynamics also freezes. The physical scenario provided by the simulations is discussed and compared against results obtained with the self-consistent generalized Langevin equation theory, and both provide a consistent description of the dynamical arrest transitions in the system. Our results are summarized in an arrested states diagram which qualitatively organizes the simulation data and provides a generic picture of the glass transitions of a dipolar fluid.

Spherical harmonic projections of the static structure factor of the dipolar hard sphere model: Theory vs simulations.

We investigate the static correlations of a dipolar fluid in terms of the irreducible coefficients of the spherical harmonic expansion of the static structure factor. To this end, we develop a theoretical framework based on a soft-core version of Wertheim's solution of the mean spherical approximation (MSA), which renders the analytical determination of such coefficients possible. The accuracy of this approximation is tested by a comparison against the results obtained with the assistance of extensive molecular dynamics simulations at different regimes of concentration and temperature. Crucial aspects for the comparison of the results provided by the two methods are carefully discussed, concerning the different reference frames used in theory and simulations to describe rotations and orientations, and leading to important differences in the behavior of correlation functions with the same combination of spherical harmonic indices. We find a remarkable agreement between the two approaches in the fluid regime, thus providing a first stringent comparison of the irreducible coefficients of the spherical harmonic expansion of the dipolar fluid's static structure factor, provided by the MSA theory and molecular dynamics simulations.

Binary colloidal glasses: linear viscoelasticity and its link to the microscopic structure and dynamics.

We study the relation between the microscopic structure and dynamics and the macroscopic rheological response of glass-forming colloidal suspensions, namely binary colloidal hard-sphere mixtures with large size asymmetry (1 : 5) that span a large range of mixture compositions close to the glass transition. The dynamical shear moduli are measured by oscillatory rheology and the structure and dynamics on the single-particle level by confocal microscopy. The data are compared with Brownian Dynamics simulations and predictions from mode-coupling theory based on the Percus-Yevick approximation. Experiments, simulations and theory consistently observe a strong decrease of the intermediate-frequency mechanical moduli combined with faster dynamics at intermediate mixing ratios and hence a non-monotonic dependence of these parameters but a localization of the large particles which decreases monotonically as the fraction of small particles is increased. We find that the Generalized-Stokes Einstein relation applied to the mean square displacements of the two components leads to a reasonable estimate of the shear moduli of the mixtures and hence links the rheological response to the particle dynamics which in turn reflects the microscopic structure.

On the dynamics of reaction coordinates in classical, time-dependent, many-body processes.

Complex microscopic many-body processes are often interpreted in terms of so-called "reaction coordinates," i.e., in terms of the evolution of a small set of coarse-grained observables. A rigorous method to produce the equation of motion of such observables is to use projection operator techniques, which split the dynamics of the observables into a main contribution and a marginal one. The basis of any derivation in this framework is the classical Heisenberg equation for an observable. If the Hamiltonian of the underlying microscopic dynamics and the observable under study do not explicitly depend on time, this equation is obtained by a straightforward derivation. However, the problem is more complicated if one considers Hamiltonians which depend on time explicitly as, e.g., in systems under external driving, or if the observable of interest has an explicit dependence on time. We use an analogy to fluid dynamics to derive the classical Heisenberg picture and then apply a projection operator formalism to derive the nonstationary generalized Langevin equation for a coarse-grained variable. We show, in particular, that the results presented for time-independent Hamiltonians and observables in the study by Meyer, Voigtmann, and Schilling, J. Chem. Phys. 147, 214110 (2017) can be generalized to the time-dependent case.

Glassy relaxation slows down by increasing mobility.

We find a striking trend reversal in the relaxation dynamics of mixtures with strong dynamical asymmetry. Simulations by both Brownian and Newtonian dynamics reveal that in mixtures of fast and slow hard spheres, above a critical density, the dynamics becomes slower upon increasing the mobility of the fast particles. Below that density, the same increase in mobility speeds up the dynamics. The critical density itself can be identified with the glass transition of the mode-coupling theory that does not depend on the dynamical asymmetry. The asymptotic dynamics close to the critical density is universal, but strong pre-asymptotic effects prevail in particular when the dynamical asymmetry also involves size asymmetry. Our observations reconcile earlier findings, where a strong dependence on kinetic parameters was found for the glassy dynamics, with the paradigm that the glass transition is determined by the properties of configuration space alone.

Clearing out a maze: A model of chemotactic motion in porous media.

We study the anomalous dynamics of a biased "hungry" (or "greedy") random walk on a percolating cluster. The model mimics chemotaxis in a porous medium: In close resemblance to the 1980s arcade game PAC-MAN®, the hungry random walker consumes food, which is initially distributed in the maze, and biases its movement towards food-filled sites. We observe that the mean-squared displacement of the process follows a power law with an exponent that is different from previously known exponents describing passive or active microswimmer dynamics. The change in dynamics is well described by a dynamical exponent that depends continuously on the propensity to move towards food. It results in slower differential growth when compared to the unbiased random walk.

On the non-stationary generalized Langevin equation.

In molecular dynamics simulations and single molecule experiments, observables are usually measured along dynamic trajectories and then averaged over an ensemble ("bundle") of trajectories. Under stationary conditions, the time-evolution of such averages is described by the generalized Langevin equation. By contrast, if the dynamics is not stationary, it is not a priori clear which form the equation of motion for an averaged observable has. We employ the formalism of time-dependent projection operator techniques to derive the equation of motion for a non-equilibrium trajectory-averaged observable as well as for its non-stationary auto-correlation function. The equation is similar in structure to the generalized Langevin equation but exhibits a time-dependent memory kernel as well as a fluctuating force that implicitly depends on the initial conditions of the process. We also derive a relation between this memory kernel and the autocorrelation function of the fluctuating force that has a structure similar to a fluctuation-dissipation relation. In addition, we show how the choice of the projection operator allows us to relate the Taylor expansion of the memory kernel to data that are accessible in MD simulations and experiments, thus allowing us to construct the equation of motion. As a numerical example, the procedure is applied to Brownian motion initialized in non-equilibrium conditions and is shown to be consistent with direct measurements from simulations.

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.

Ex-vivo validation of spatial gain sonography for the quantification of echo intensity in fascicle-aligned ultrasound images in ten anatomical muscles in Bos taurus.

This study aimed to validate the concept of spatial gain sonography for quantifying texture-related echo intensity in B-mode ultrasound of skeletal muscle. Fifty-one bovine muscles were scanned postmortem using B-mode ultrasonography at varying fascicle probe angles (FPA). The relationship between mean gray values (MGV) and FPA was fitted with a sinusoidal and a linear function, the slope of which was defined as tilt echo gain (TEG). Macroscopic muscle cross sections were optically analyzed for intramuscular connective tissue (IMCT) content which was plotted against MGV at 0° FPA (MGV_00). MGV peaked at FPA 0°. Sine fits were superior to linear fits (adjusted r2-values 0.647 vs. 0.613), especially for larger FPAs. In mixed models, the pennation angle was related to TEG (P < 0.001) and MGV_00 (P = 0.035). Age was relevant for MGV_00 (P < 0.001), but not TEG (P > 0.10). The correlation between the IMCT percentage and MGV_00 was significant but weak (P = 0.026; adjusted r2 = 0.103). The relationship between fascicle probe angle and echo intensity in B-mode ultrasound can be modeled more accurately with a sinusoidal but more practically for clinical use with a linear fit. The peak mean gray value MGV_00 can be used to compare echo intensity across muscles without the bias of pennation angle.

On the Bauschinger effect in supercooled melts under shear: results from mode coupling theory and molecular dynamics simulations.

We study the nonlinear rheology of a glass-forming binary mixture under the reversal of shear flow using molecular dynamics simulations and a schematic model of the mode-coupling theory of the glass transition (MCT). Memory effects lead to a history-dependent response, as exemplified by the vanishing of a stress-overshoot phenomenon in the stress-strain curves of the sheared liquid, and a change in the apparent elastic coefficients around states with zero stress. We investigate the various retarded contributions to the stress response at a given time schematically within MCT. The connection of this macroscopic response to single-particle motion is demonstrated using molecular-dynamics simulation.

Curvature of gastrocnemius muscle fascicles as function of muscle-tendon complex length and contraction in humans.

It has been shown that muscle fascicle curvature increases with increasing contraction level and decreasing muscle-tendon complex length. The analyses were done with limited examination windows concerning contraction level, muscle-tendon complex length, and/or intramuscular position of ultrasound imaging. With this study we aimed to investigate the correlation between fascicle arching and contraction, muscle-tendon complex length and their associated architectural parameters in gastrocnemius muscles to develop hypotheses concerning the fundamental mechanism of fascicle curving. Twelve participants were tested in five different positions (90°/105°*, 90°/90°*, 135°/90°*, 170°/90°*, and 170°/75°*; *knee/ankle angle). They performed isometric contractions at four different contraction levels (5%, 25%, 50%, and 75% of maximum voluntary contraction) in each position. Panoramic ultrasound images of gastrocnemius muscles were collected at rest and during constant contraction. Aponeuroses and fascicles were tracked in all ultrasound images and the parameters fascicle curvature, muscle-tendon complex strain, contraction level, pennation angle, fascicle length, fascicle strain, intramuscular position, sex and age group were analyzed by linear mixed effect models. Mean fascicle curvature of the medial gastrocnemius increased with contraction level (+5 m-1 from 0% to 100%; p = 0.006). Muscle-tendon complex length had no significant impact on mean fascicle curvature. Mean pennation angle (2.2 m-1 per 10°; p < 0.001), inverse mean fascicle length (20 m-1 per cm-1 ; p = 0.003), and mean fascicle strain (-0.07 m-1 per +10%; p = 0.004) correlated with mean fascicle curvature. Evidence has also been found for intermuscular, intramuscular, and sex-specific intramuscular differences of fascicle curving. Pennation angle and the inverse fascicle length show the highest predictive capacities for fascicle curving. Due to the strong correlations between pennation angle and fascicle curvature and the intramuscular pattern of curving we suggest for future studies to examine correlations between fascicle curvature and intramuscular fluid pressure.

Glass rheology: From mode-coupling theory to a dynamical yield criterion.

The mode coupling theory (MCT) of glasses, while offering an incomplete description of glass transition physics, represents the only established route to first-principles prediction of rheological behavior in nonergodic materials such as colloidal glasses. However, the constitutive equations derivable from MCT are somewhat intractable, hindering their practical use and also their interpretation. Here, we present a schematic (single-mode) MCT model which incorporates the tensorial structure of the full theory. Using it, we calculate the dynamic yield surface for a large class of flows.

Spreading of droplets under various gravitational accelerations.

We describe a setup to perform systematic studies on the spreading of droplets of complex fluids under microgravity conditions. Tweaking the gravitational acceleration under which droplets are deposited provides access to different regimes of the spreading dynamics, as quantified through the Bond number. In particular, microgravity allows us to form large droplets while remaining in the regime where surface tension effects and internal driving stresses are predominant over hydrostatic forces. The vip-drop2 (visco-plastic droplets on the drop tower) experimental module provides a versatile platform to study a wide range of complex fluids through the deposition of axisymmetric droplets. The module offers the possibility to deposit droplets on a precursor layer, which can be composed of the same or a different fluid. Furthermore, it allows us to deposit four droplets simultaneously while conducting shadowgraphy on all of them and observing either the flow field (through particle image velocimetry) or the stress distribution inside the droplet in the case of stress birefringent fluids. It was developed for a drop tower catapult system, is designed to withstand a vertical acceleration of up to 30 times the Earth's gravitational acceleration in the downward direction, and is capable of operating remotely under microgravity conditions. We provide a detailed description of the module and an exemplary data analysis for droplets spreading on-ground and in microgravity.

Machine learning interatomic potentials for aluminium: application to solidification phenomena.

In studying solidification process by simulations on the atomic scale, the modeling of crystal nucleation or amorphization requires the construction of interatomic interactions that are able to reproduce the properties of both the solid and the liquid states. Taking into account rare nucleation events or structural relaxation under deep undercooling conditions requires much larger length scales and longer time scales than those achievable byab initiomolecular dynamics (AIMD). This problem is addressed by means of classical molecular dynamics simulations using a well established high dimensional neural network potential trained on a set of configurations generated by AIMD relevant for solidification phenomena. Our dataset contains various crystalline structures and liquid states at different pressures, including their time fluctuations in a wide range of temperatures. Applied to elemental aluminium, the resulting potential is shown to be efficient to reproduce the basic structural, dynamics and thermodynamic quantities in the liquid and undercooled states. Early stages of crystallization are further investigated on a much larger scale with one million atoms, allowing us to unravel features of the homogeneous nucleation mechanisms in the fcc phase at ambient pressure as well as in the bcc phase at high pressure with unprecedented accuracy close to theab initioone. In both cases, a single step nucleation process is observed.