Elasticity, Facilitation, and Dynamic Heterogeneity in Glass-Forming Liquids.

We study the role of elasticity-induced facilitation on the dynamics of glass-forming liquids by a coarse-grained two-dimensional model in which local relaxation events, taking place by thermal activation, can trigger new relaxations by long-range elastically mediated interactions. By simulations and an analytical theory, we show that the model reproduces the main salient facts associated with dynamic heterogeneity and offers a mechanism to explain the emergence of dynamical correlations at the glass transition. We also discuss how it can be generalized and combined with current theories.

Finite-Disorder Critical Point in the Yielding Transition of Elastoplastic Models.

Upon loading, amorphous solids can exhibit brittle yielding, with the abrupt formation of macroscopic shear bands leading to fracture, or ductile yielding, with a multitude of plastic events leading to homogeneous flow. It has been recently proposed, and subsequently questioned, that the two regimes are separated by a sharp critical point, as a function of some control parameter characterizing the intrinsic disorder strength and the degree of stability of the solid. In order to resolve this issue, we have performed extensive numerical simulations of athermally driven elastoplastic models with long-range and anisotropic realistic interaction kernels in two and three dimensions. Our results provide clear evidence for a finite-disorder critical point separating brittle and ductile yielding, and we provide an estimate of the critical exponents in 2D and 3D.

Random critical point separates brittle and ductile yielding transitions in amorphous materials.

We combine an analytically solvable mean-field elasto-plastic model with molecular dynamics simulations of a generic glass former to demonstrate that, depending on their preparation protocol, amorphous materials can yield in two qualitatively distinct ways. We show that well-annealed systems yield in a discontinuous brittle way, as metallic and molecular glasses do. Yielding corresponds in this case to a first-order nonequilibrium phase transition. As the degree of annealing decreases, the first-order character becomes weaker and the transition terminates in a second-order critical point in the universality class of an Ising model in a random field. For even more poorly annealed systems, yielding becomes a smooth crossover, representative of the ductile rheological behavior generically observed in foams, emulsions, and colloidal glasses. Our results show that the variety of yielding behaviors found in amorphous materials does not necessarily result from the diversity of particle interactions or microscopic dynamics but is instead unified by carefully considering the role of the initial stability of the system.

Ultrastable Metallic Glasses In Silico.

We develop a generic strategy and simple numerical models for multicomponent metallic glasses for which the swap Monte Carlo algorithm can produce highly stable equilibrium configurations equivalent to experimental systems cooled more than 10^{7} times slower than in conventional simulations. This paves the way for a deeper understanding of the thermodynamic, dynamic, and mechanical properties of metallic glasses. As first applications, we considerably extend configurational entropy measurements down to the experimental glass temperature, and demonstrate a qualitative change of the mechanical response of metallic glasses of increasing stability toward brittleness.

Glass Stability Changes the Nature of Yielding under Oscillatory Shear.

We perform molecular dynamics simulations to investigate the effect of a glass preparation on its yielding transition under oscillatory shear. We use swap Monte Carlo to investigate a broad range of glass stabilities from poorly annealed to highly stable systems. We observe a qualitative change in the nature of yielding, which evolves from ductile to brittle as glass stability increases. Our results disentangle the relative role of mechanical and thermal annealing on the mechanical properties of amorphous solids, which is relevant for various experimental situations from the rheology of soft materials to fatigue failure in metallic glasses.

Configurational entropy measurements in extremely supercooled liquids that break the glass ceiling.

Liquids relax extremely slowly on approaching the glass state. One explanation is that an entropy crisis, because of the rarefaction of available states, makes it increasingly arduous to reach equilibrium in that regime. Validating this scenario is challenging, because experiments offer limited resolution, while numerical studies lag more than eight orders of magnitude behind experimentally relevant timescales. In this work, we not only close the colossal gap between experiments and simulations but manage to create in silico configurations that have no experimental analog yet. Deploying a range of computational tools, we obtain four estimates of their configurational entropy. These measurements consistently confirm that the steep entropy decrease observed in experiments is also found in simulations, even beyond the experimental glass transition. Our numerical results thus extend the observational window into the physics of glasses and reinforce the relevance of an entropy crisis for understanding their formation.

Configurational entropy of glass-forming liquids.

The configurational entropy is one of the most important thermodynamic quantities characterizing supercooled liquids approaching the glass transition. Despite decades of experimental, theoretical, and computational investigation, a widely accepted definition of the configurational entropy is missing, its quantitative characterization remains fraught with difficulties, misconceptions, and paradoxes, and its physical relevance is vividly debated. Motivated by recent computational progress, we offer a pedagogical perspective on the configurational entropy in glass-forming liquids. We first explain why the configurational entropy has become a key quantity to describe glassy materials, from early empirical observations to modern theoretical treatments. We explain why practical measurements necessarily require approximations that make its physical interpretation delicate. We then demonstrate that computer simulations have become an invaluable tool to obtain precise, nonambiguous, and experimentally relevant measurements of the configurational entropy. We describe a panel of available computational tools, offering for each method a critical discussion. This perspective should be useful to both experimentalists and theoreticians interested in glassy materials and complex systems.

Does the Adam-Gibbs relation hold in simulated supercooled liquids?

We perform stringent tests of thermodynamic theories of the glass transition over the experimentally relevant temperature regime for several simulated glass-formers. The swap Monte Carlo algorithm is used to estimate the configurational entropy and static point-to-set lengthscale, and careful extrapolations are used for the relaxation times. We first quantify the relation between configurational entropy and the point-to-set lengthscale in two and three dimensions. We then show that the Adam-Gibbs relation is generally violated in simulated models for the experimentally relevant time window. Collecting experimental data for several supercooled molecular liquids, we show that the same trends are observed experimentally. Deviations from the Adam-Gibbs relation remain compatible with random first order transition theory and may account for the reported discrepancies between Kauzmann and Vogel-Fulcher-Tammann temperatures. Alternatively, they may also indicate that even near Tg thermodynamics is not the only driving force for slow dynamics.

Ideal Glass States Are Not Purely Vibrational: Insight from Randomly Pinned Glasses.

We use computer simulations to probe the thermodynamic and dynamic properties of a glass former that undergoes an ideal glass transition because of the presence of randomly pinned particles. We find that even deep in the equilibrium glass state, the system relaxes to some extent because of the presence of localized excitations that allow the system to access different inherent structures, thus giving rise to a nontrivial contribution to the entropy. By calculating with high accuracy the vibrational part of the entropy, we show that also in the equilibrium glass state thermodynamics and dynamics give a coherent picture, and that glasses should not be seen as a disordered solid in which the particles undergo just vibrational motion but instead as a system with a highly nonlinear internal dynamics.

Dynamic and thermodynamic crossover scenarios in the Kob-Andersen mixture: Insights from multi-CPU and multi-GPU simulations.

The physical behavior of glass-forming liquids presents complex features of both dynamic and thermodynamic nature. Some studies indicate the presence of thermodynamic anomalies and of crossovers in the dynamic properties, but their origin and degree of universality is difficult to assess. Moreover, conventional simulations are barely able to cover the range of temperatures at which these crossovers usually occur. To address these issues, we simulate the Kob-Andersen Lennard-Jones mixture using efficient protocols based on multi-CPU and multi-GPU parallel tempering. Our setup enables us to probe the thermodynamics and dynamics of the liquid at equilibrium well below the critical temperature of the mode-coupling theory, [Formula: see text]. We find that below [Formula: see text] the analysis is hampered by partial crystallization of the metastable liquid, which nucleates extended regions populated by large particles arranged in an fcc structure. By filtering out crystalline samples, we reveal that the specific heat grows in a regular manner down to [Formula: see text] . Possible thermodynamic anomalies suggested by previous studies can thus occur only in a region of the phase diagram where the system is highly metastable. Using the equilibrium configurations obtained from the parallel tempering simulations, we perform molecular dynamics and Monte Carlo simulations to probe the equilibrium dynamics down to [Formula: see text]. A temperature-derivative analysis of the relaxation time and diffusion data allows us to assess different dynamic scenarios around [Formula: see text]. Hints of a dynamic crossover come from analysis of the four-point dynamic susceptibility. Finally, we discuss possible future numerical strategies to clarify the nature of crossover phenomena in glass-forming liquids.

Configurational entropy of polydisperse supercooled liquids.

We propose a computational method to measure the configurational entropy in generic polydisperse glass-formers. In particular, our method resolves issues related to the diverging mixing entropy term due to a continuous polydispersity. The configurational entropy is measured as the difference between the well-defined fluid entropy and a more problematic glass entropy. We show that the glass entropy can be computed by a simple generalisation of the Frenkel-Ladd thermodynamic integration method, which takes into account permutations of the particle diameters. This approach automatically provides a physically meaningful mixing entropy for the glass entropy and includes contributions that are not purely vibrational. The proposed configurational entropy is thus devoid of conceptual and technical difficulties due to continuous polydispersity, while being conceptually closer, but technically simpler, than alternative free energy approaches.

Equilibrium phase diagram of a randomly pinned glass-former.

We use computer simulations to study the thermodynamic properties of a glass-former in which a fraction c of the particles has been permanently frozen. By thermodynamic integration, we determine the Kauzmann, or ideal glass transition, temperature [Formula: see text] at which the configurational entropy vanishes. This is done without resorting to any kind of extrapolation, i.e., [Formula: see text] is indeed an equilibrium property of the system. We also measure the distribution function of the overlap, i.e., the order parameter that signals the glass state. We find that the transition line obtained from the overlap coincides with that obtained from the thermodynamic integration, thus showing that the two approaches give the same transition line. Finally, we determine the geometrical properties of the potential energy landscape, notably the T- and c dependence of the saddle index, and use these properties to obtain the dynamic transition temperature [Formula: see text]. The two temperatures [Formula: see text] and [Formula: see text] cross at a finite value of c and indicate the point at which the glass transition line ends. These findings are qualitatively consistent with the scenario proposed by the random first-order transition theory.

Does the configurational entropy of polydisperse particles exist?

Classical particle systems characterized by continuous size polydispersity, such as colloidal materials, are not straightforwardly described using statistical mechanics, since fundamental issues may arise from particle distinguishability. Because the mixing entropy in such systems is divergent in the thermodynamic limit, we show that the configurational entropy estimated from standard computational approaches to characterize glassy states also diverges. This reasoning would suggest that polydisperse materials cannot undergo a glass transition, in contradiction to experiments. We explain that this argument stems from the confusion between configurations in phase space and states defined by free energy minima, and propose a simple method to compute a finite and physically meaningful configurational entropy in continuously polydisperse systems. Physically, the proposed approach relies on an effective description of the system as an M*-component system with a finite M*, for which finite mixing and configurational entropies are obtained. We show how to directly determine M* from computer simulations in a range of glass-forming models with different size polydispersities, characterized by hard and soft interparticle interactions, and by additive and non-additive interactions. Our approach provides consistent results in all cases and demonstrates that the configurational entropy of polydisperse system exists, is finite, and can be quantitatively estimated.

Equilibrium Sampling of Hard Spheres up to the Jamming Density and Beyond.

We implement and optimize a particle-swap Monte Carlo algorithm that allows us to thermalize a polydisperse system of hard spheres up to unprecedentedly large volume fractions, where previous algorithms and experiments fail to equilibrate. We show that no glass singularity intervenes before the jamming density, which we independently determine through two distinct nonequilibrium protocols. We demonstrate that equilibrium fluid and nonequilibrium jammed states can have the same density, showing that the jamming transition cannot be the end point of the fluid branch.

Creating bulk ultrastable glasses by random particle bonding.

A recent breakthrough in glass science has been the synthesis of ultrastable glasses via physical vapor deposition techniques. These samples display enhanced thermodynamic, kinetic and mechanical stability, with important implications for fundamental science and technological applications. However, the vapor deposition technique is limited to atomic, polymer and organic glass-formers and is only able to produce thin film samples. Here, we propose a novel approach to generate ultrastable glassy configurations in the bulk, via random particle bonding, and using computer simulations we show that this method does indeed allow for the production of ultrastable glasses. Our technique is in principle applicable to any molecular or soft matter system, such as colloidal particles with tunable bonding interactions, thus opening the way to the design of a large class of ultrastable glasses.

Jamming transition and inherent structures of hard spheres and disks.

Recent studies show that volume fractions φ(J) at the jamming transition of frictionless hard spheres and disks are not uniquely determined but exist over a continuous range. Motivated by this observation, we numerically investigate the dependence of φ(J) on the initial configurations of the parent fluid equilibrated at a volume fraction φ(eq), before compressing to generate a jammed packing. We find that φ(J) remains constant when φ(eq) is small but sharply increases as φ(eq) exceeds the dynamic transition point which the mode-coupling theory predicts. We carefully analyze configurational properties of both jammed packings and parent fluids and find that, while all jammed packings remain isostatic, the increase of φ(J) is accompanied with subtle but distinct changes of local orders, a static length scale, and an exponent of the finite-size scaling. These results are consistent with the scenario of the random first-order transition theory of the glass transition.

Zero-temperature glass transition in two dimensions.

Liquids cooled towards the glass transition temperature transform into amorphous solids that have a wide range of applications. While the nature of this transformation is understood rigorously in the mean-field limit of infinite spatial dimensions, the problem remains wide open in physical dimensions. Nontrivial finite-dimensional fluctuations are hard to control analytically, and experiments fail to provide conclusive evidence regarding the nature of the glass transition. Here, we develop Monte Carlo methods for two-dimensional glass-forming liquids that allow us to access equilibrium states at sufficiently low temperatures to directly probe the glass transition in a regime inaccessible to experiments. We find that the liquid state terminates at a thermodynamic glass transition which occurs at zero temperature and is associated with an entropy crisis and a diverging static correlation length. Our results thus demonstrate that a thermodynamic glass transition can occur in finite dimensional glass-formers.

Local order and crystallization of dense polydisperse hard spheres.

Computer simulations give precious insight into the microscopic behavior of supercooled liquids and glasses, but their typical time scales are orders of magnitude shorter than the experimentally relevant ones. We recently closed this gap for a class of models of size polydisperse fluids, which we successfully equilibrate beyond laboratory time scales by means of the swap Monte Carlo algorithm. In this contribution, we study the interplay between compositional and geometric local orders in a model of polydisperse hard spheres equilibrated with this algorithm. Local compositional order has a weak state dependence, while local geometric order associated to icosahedral arrangements grows more markedly but only at very high density. We quantify the correlation lengths and the degree of sphericity associated to icosahedral structures and compare these results to those for the Wahnström Lennard-Jones mixture. Finally, we analyze the structure of very dense samples that partially crystallized following a pattern incompatible with conventional fractionation scenarios. The crystal structure has the symmetry of aluminum diboride and involves a subset of small and large particles with size ratio approximately equal to 0.5.