Ludovic Berthier

Theoretical perspective on the glass transition and amorphous materials

A theoretical perspective is provided on the glass transition in molecular liquids at thermal equilibrium, on the spatially heterogeneous and aging dynamics of disordered materials, and on the rheology of soft glassy materials. We start with a broad introduction to the field and emphasize its connections with other subjects and its relevance. The important role played by computer simulations in studying and understanding the dynamics of systems close to the glass transition at the molecular level is given. The recent progress on the subject of the spatially heterogeneous dynamics that characterizes structural relaxation in materials with slow dynamics is reviewed. The main theoretical approaches are presented describing the glass transition in supercooled liquids, focusing on theories that have a microscopic, statistical mechanics basis. We describe both successes and failures and critically assess the current status of each of these approaches. The physics of aging dynamics in disordered materials and the rheology of soft glassy materials are then discussed, and recent theoretical progress is described. For each section, an extensive overview is given of the most recent advances, but we also describe in some detail the important open problems that will occupy a central place in this field in the coming years.

Direct experimental evidence of a growing length scale accompanying the glass transition

Understanding glass formation is a challenge, because the existence of a true glass state, distinct from liquid and solid, remains elusive: Glasses are liquids that have become too viscous to flow. An old idea, as yet unproven experimentally, is that the dynamics becomes sluggish as the glass transition approaches, because increasingly larger regions of the material have to move simultaneously to allow flow. We introduce new multipoint dynamical susceptibilities to estimate quantitatively the size of these regions and provide direct experimental evidence that the glass formation of molecular liquids and colloidal suspensions is accompanied by growing dynamic correlation length scales.

Dynamical heterogeneities in glasses, colloids, and granular media

1. Scientic interview on the glass transition 2. An overview of the theories of the glass transition 3. Overview of different characterisations of dynamic heterogeneity 4. Glassy dynamics and dynamical heterogeneity in colloids 5. Experimental Approaches to Heterogeneous Dynamics 6. Dynamical Heterogeneities in Grains and Foams 7. The Length Scales of Dynamic Heterogeneity: Results from Molecular Dynamics Simulations 8. Heterogeneities in amorphous systems under shear 9. The jamming scenario an introduction and outlook 10. Kinetically Constrained Models 11. Growing length scales in aging systems 12. Analytical approaches to time and length scales in models of glasses

Probing the Equilibrium Dynamics of Colloidal Hard Spheres above the Mode-Coupling Glass Transition

We use dynamic light scattering and computer simulations to study equilibrium dynamics and dynamic heterogeneity in concentrated suspensions of colloidal hard spheres. Our study covers an unprecedented density range and spans seven decades in structural relaxation time, � � , including equilibrium measurements above ’c, the location of the glass transition deduced from fitting our data to mode-coupling theory. Instead of falling out of equilibrium, the system remains ergodic above ’c and enters a new dynamical regime where � � increases with a functional form that was not anticipated by previous experiments, while the amplitude of dynamic heterogeneity grows slower than a power law with � � , as found in molecular glass formers close to the glass transition.

Universal Nature of Particle Displacements close to Glass and Jamming Transitions

We examine the structure of the distribution of single particle displacements (van Hove function) in a broad class of materials close to glass and jamming transitions. In a wide time window comprising structural relaxation, van Hove functions reflect the coexistence of slow and fast particles (dynamic heterogeneity). The tails of the distributions exhibit exponential, rather than Gaussian, decay. We argue that this behavior is universal in glassy materials and should be considered the analog, in space, of the stretched exponential decay of time correlation functions. We introduce a dynamical model that describes quantitatively numerical and experimental data in supercooled liquids, colloidal hard spheres, and granular materials. The tails of the distributions directly explain the decoupling between translational diffusion and structural relaxation observed in glassy materials.

Spatial correlations in the dynamics of glassforming liquids : Experimental determination of their temperature dependence

We use recently introduced three-point dynamic susceptibilities to obtain an experimental determination of the temperature evolution of the number of molecules Ncorr that are dynamically correlated during the structural relaxation of supercooled liquids. We first discuss in detail the physical content of three-point functions that relate the sensitivity of the averaged two-time dynamics to external control parameters (such as temperature or density), as well as their connection to the more standard four-point dynamic susceptibility associated with dynamical heterogeneities. We then demonstrate that these functions can be experimentally determined with good precision. We gather available data to obtain the temperature dependence of Ncorr for a large number of supercooled liquids over a wide range of relaxation time scales from the glass transition up to the onset of slow dynamics. We find that Ncorr systematically grows when approaching the glass transition. It does so in a modest manner close to the glass transition, which is consistent with an activation-based picture of the dynamics in glassforming materials. For higher temperatures, there appears to be a regime where Ncorr behaves as a power-law of the relaxation time. Finally, we find that the dynamic response to density, while being smaller than the dynamic response to temperature, behaves similarly, in agreement with theoretical expectations.

Spontaneous and induced dynamic fluctuations in glass-formers I: General results and dependence on ensemble and dynamics

We study theoretically and numerically a family of multipoint dynamic susceptibilities that quantify the strength and characteristic length scales of dynamic heterogeneities in glass-forming materials. We use general theoretical arguments (fluctuation-dissipation relations and symmetries of relevant dynamical field theories) to relate the sensitivity of averaged two-time correlators to temperature and density to spontaneous fluctuations of the local dynamics. Our theoretical results are then compared to molecular dynamics simulations of the Newtonian, Brownian, and Monte Carlo dynamics of two representative glass-forming liquids, a fragile binary Lennard-Jones mixture, and a model for the strong glass-former silica. We justify in detail the claim made by Berthier et al. [Science 310, 1797 (2005)] that the temperature dependence of correlation functions allows one to extract useful information on dynamic length scales in glassy systems. We also discuss some subtle issues associated with the choice of microscopic dynamics and of statistical ensemble through conserved quantities, which are found to play an important role in determining dynamic correlations.

Dynamical susceptibility of glass formers: Contrasting the predictions of theoretical scenarios

We compute analytically and numerically the four-point correlation function that characterizes non-trivial cooperative dynamics in glassy systems within several models of glasses: elasto-plastic deformations, mode-coupling theory (MCT), collectively rearranging regions (CRR), diffusing defects and kinetically constrained models (KCM). Some features of the four-point susceptibility chi_4(t) are expected to be universal. at short times we expect an elastic regime characterized by a t or sqrt{t} growth. We find both in the beta, and the early alpha regime that chi_4 sim t^mu, where mu is directly related to the mechanism responsible for relaxation. This regime ends when a maximum of chi_4 is reached at a time t=t^* of the order of the relaxation time of the system. This maximum is followed by a fast decay to zero at large times. The height of the maximum also follows a power-law, chi_4(t^*) sim t^{*lambda}. The value of the exponents mu and lambda allows one to distinguish between different mechanisms. For example, freely diffusing defects in d=3 lead to mu=2 and lambda=1, whereas the CRR scenario rather predicts either mu=1 or a logarithmic behaviour depending on the nature of the nucleation events, and a logarithmic behaviour of chi_4(t^*). MCT leads to mu=b and lambda =1/gamma, where b and gamma are the standard MCT exponents. We compare our theoretical results with numerical simulations on a Lennard-Jones and a soft-sphere system. Within the limited time-scales accessible to numerical simulations, we find that the exponent mu is rather small, mu<1, with a value in reasonable agreement with the MCT predictions.

Nonequilibrium dynamics and fluctuation-dissipation relation in a sheared fluid

The nonequilibrium dynamics of a binary Lennard-Jones mixture in a simple shear flow is investigated by means of molecular dynamics simulations. The range of temperature T investigated covers both the liquid, supercooled, and glassy states, while the shear rate γ covers both the linear and nonlinear regimes of rheology. The results can be interpreted in the context of a nonequilibrium, schematic mode-coupling theory developed recently, which makes the theory applicable to a wide range of soft glassy materials. The behavior of the viscosity η(T,γ) is first investigated. In the nonlinear regime, strong shear-thinning is obtained, η∼γ−α(T), with α(T)≃23 in the supercooled regime. Scaling properties of the intermediate scattering functions are studied. Standard “mode-coupling properties” of factorization and time superposition hold in this nonequilibrium situation. The fluctuation-dissipation relation is violated in the shear flow in a way very similar to that predicted theoretically, allowing for the definit...

Shear localization in a model glass

Using molecular dynamics simulations, we show that a simple model of a glassy material exhibits the shear localization phenomenon observed in many complex fluids. At low shear rates, the system separates into a fluidized shear band and an unsheared part. The two bands are characterized by a very different dynamics probed by a local intermediate scattering function. Furthermore, a stick-slip motion is observed at very small shear rates. Our results, which open the possibility of exploring complex rheological behavior using simulations, are compared to recent experiments on various soft glasses.