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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 t w = 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 (t w > 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.

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.

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.

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.

A fundamental challenge of the theory of liquids is to understand the similarities and differences in the macroscopic dynamics of both colloidal and atomic liquids, which originate in the (Newtonian or Brownian) nature of the microscopic motion of their constituents. Starting from the recently-discovered long-time dynamic equivalence between a colloidal and an atomic liquid that share the same interparticle pair potential, in this work we develop a self-consistent generalized Langevin equation (SCGLE) theory for the dynamics of equilibrium multicomponent atomic liquids, applicable as an approximate but quantitative theory describing the long-time diffusive dynamical properties of simple equilibrium atomic liquids. When complemented with a Gaussian-like approximation, this theory is also able to provide a reasonable representation of the passage from ballistic to diffusive behavior. We illustrate the applicability of the resulting theory with three particular examples, namely, a monodisperse and a polydisperse monocomponent hard-sphere liquid, and a highly size-asymmetric binary hard-sphere mixture. To assess the quantitative accuracy of our results, we perform event-driven molecular dynamics simulations, which corroborate the general features of the theoretical predictions., Comment: 11 pages, 12 Figures