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 tw), depending on the depth of the quench from the liquid into the glass: "simple" aging (τ∼tw) applies for quenches close to the critical point of mode-coupling theory (MCT) and implies "subaging" (τ≈tδw with δ1) 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 β-relaxation theory (SBR). We exemplify the scaling laws with a schematic model that quantitatively fits simulation data

Inner clocks of glass-forming fluids

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

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 (softcore) 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 ({$\eta$} = 0.2) and intermediate (${\eta}$ = 0.4) volume fractions, both dynamics are strongly coupled and become simultaneously arrested upon cooling. At high concentrations ({$\eta$} $\lt$ 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

Glassy dynamics in asymmetric binary mixtures of hard-spheres

The binary hard-sphere mixture is one of the simplest representations of a many-body system with competing time and length scales. This model is relevant to fundamentally understand both the structural and dynamical properties of materials, such as metallic melts, colloids, polymers and bio-based composites. It also allows us to study how different scales influence the physical behavior of a multicomponent glass-forming liquid; a question that still awaits a unified description. In this contribution, we report on distinct dynamical arrest transitions in highly asymmetric binary colloidal mixtures, namely, a single glass of big particles, in which the small species remains ergodic, and a double glass with the simultaneous arrest of both components. When the mixture approaches any glass transition, the relaxation of the collective dynamics of both species becomes coupled. In the single glass domain, spatial modulations occur due to the structure of the large spheres, a feature not observed in the two-glass domain. The relaxation of the \emph{self} dynamics of small and large particles, in contrast, become decoupled at the boundaries of both transitions; the large species always displays dynamical arrest, whereas the small ones appear arrested only in the double glass. Thus, in order to obtain a complete picture of the distinct glassy states, one needs to take into account the dynamics of both species

Self-consistent generalized Langevin equation theory for liquids of non-spherical brownian particles

"A theoretical approach is proposed in order to describe, in the absence of hydrodynamic interactions, the equilibrium self and collective dynamics of brownian liquids conformed by non-spherical interacting particles. As an extension of the so-called self-consistent generalized Langevin equation formalism (SCGLE), we derive equations of motion for the spherical harmonics projections of the collective and self intermediate scattering functions, Flm;lm(k; t) and FS lm;lm(k; t). In the long-time asymptotic limit, these equations become the socalled bifurcation equations, whose solutions (the nonergodicity parameters) can be written, extending the spherical case, in terms of one translational and one orientational scalar dynamic order parameters, gT and gR, which characterize the possible dynamical arrest transitions of a given system. As concrete and ilustrative applications of our derivations we consider two model systems, namely, a dipolar hard sphere fluid, for which we determine the arrested phases diagram; and a classical Heisenberg dipolar system with positional disorder, for which we solve the full rotational dynamics to characterize spin glass transitions.

Glass-transition asymptotics in two theories of glassy dynamics: Self-consistent generalized Langevin equation and mode-coupling theory

We contrast the generic features of structural relaxation close to the idealized glass transition that are predicted by the self-consistent generalized Langevin equation theory (SCGLE) against those that are predicted by the mode-coupling theory of the glass transition (MCT). We present an asymptotic solution close to conditions of kinetic arrest that is valid for both theories, despite the different starting points that are adopted in deriving them. This in particular provides the same level of understanding of the asymptotic dynamics in the SCGLE as was previously done only for MCT. We discuss similarities and different predictions of the two theories for kinetic arrest in standard glass-forming models, as exemplified through the hard-sphere system. Qualitative differences are found for models where a decoupling of relaxation modes is predicted, such as the generalized Gaussian core model, or binary hard-sphere mixtures of particles with very disparate sizes. These differences, which arise in the distinct treatment of the memory kernels associated to self- and collective motion of particles, lead to distinct scenarios that are predicted by each theory for partially arrested states and in the vicinity of higher-order glass-transition singularities

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

Non-equilibrium relaxation and aging in the dynamics of a dipolar fluid quenched towards the glass transition

The recently developed non-equilibrium self-consistent generalized Langevin equation theory of the dynamics of liquids of non-spherically interacting particles [2016 J. Phys. Chem. B 120 7975] is applied to the description of the irreversible relaxation of a thermally and mechanically quenched dipolar fluid. Specifically, we consider a dipolar hard-sphere liquid quenched (at tw = 0) from full equilibrium conditions towards different ergodic–non-ergodic transitions. Qualitatively different scenarios are predicted by the theory for the time evolution of the system after the quench (tw > 0), that depend on both the kind of transition approached and the specific features of the protocol of preparation. Each of these scenarios is characterized by the kinetics displayed by a set of structural correlations, and also by the development of two characteristic times describing the relaxation of the translational and rotational dynamics, allowing us to highlight the crossover from equilibration to aging in the system and leading to the prediction of different underlying mechanisms and relaxation laws for the dynamics at each of the glass transitions explored