Self-consistent Generalized Langevin Equation Theory Research Articles

Non-equilibrium view of the amorphous solidification of liquids with competing interactions.

The interplay between short-range attractions and long-range repulsions (SALR) characterizes the so-called liquids with competing interactions, which are known to exhibit a variety of equilibrium and non-equilibrium phases. The theoretical description of the phenomenology associated with glassy or gel states in these systems has to take into account both the presence of thermodynamic instabilities (such as those defining the spinodal line and the so called λ line) and the limited capability to describe genuine non-equilibrium processes from first principles. Here, we report the first application of the non-equilibrium self-consistent generalized Langevin equation theory to the description of the dynamical arrest processes that occur in SALR systems after being instantaneously quenched into a state point in the regions of thermodynamic instability. The physical scenario predicted by this theory reveals an amazing interplay between the thermodynamically driven instabilities, favoring equilibrium macro- and micro-phase separation, and the kinetic arrest mechanisms, favoring non-equilibrium amorphous solidification of the liquid into an unexpected variety of glass and gel states.

Phase separation and dynamical arrest of protein solutions dominated by short-range attractions.

The interplay of liquid-liquid phase separation (LLPS) and dynamical arrest can lead to the formation of gels and glasses, which is relevant for such diverse fields as condensed matter physics, materials science, food engineering, and the pharmaceutical industry. In this context, protein solutions exhibit remarkable equilibrium and non-equilibrium behaviors. In the regime where attractive and repulsive forces compete, it has been demonstrated, for example, that the location of the dynamical arrest line seems to be independent of ionic strength, so that the arrest lines at different ionic screening lengths overlap, in contrast to the LLPS coexistence curves, which strongly depend on the salt concentration. In this work, we show that the same phenomenology can also be observed when the electrostatic repulsions are largely screened, and the range and strength of the attractions are varied. In particular, using lysozyme in brine as a model system, the metastable gas-liquid binodal and the dynamical arrest line as well as the second virial coefficient have been determined for various solution conditions by cloud-point measurements, optical microscopy, centrifugation experiments, and light scattering. With the aim of understanding this new experimental phenomenology, we apply the non-equilibrium self-consistent generalized Langevin equation theory to a simple model system with only excluded volume plus short-range attractions, to study the dependence of the predicted arrest lines on the range of the attractive interaction. The theoretical predictions find a good qualitative agreement with experiments when the range of the attraction is not too small compared with the size of the protein.

"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.

On the dynamically arrested states of equilibrium and non-equilibrium gels: a comprehensive Brownian dynamics study

In this work a systematic study over a wide number of final thermodynamic states for two gel-forming liquids was performed. Such two kind of gel formers are distinguished by their specific interparticle interaction potential. We explored several thermodynamic states determining the thermodynamic, structural and dynamic properties of both liquids after a sudden temperature change. The thermodynamic analysis allows to identify that the liquid with short range attraction and long range repulsion lacks of a stable gas–liquid phase separation liquid, in contrast with the liquid with short range attractions. Thus, although for some thermodynamic states the structural behavior, measured by the static structure factor, is similar to and characteristic of the gel phase, for the short range attractive fluid the gel phase is a consequence of a spinodal decomposition process. In contrast, gelation in the short range attraction and long range repulsion liquid is not due to a phase separation. We also analyze the similarities and differences of the dynamic behavior of both systems through the analysis of the mean square displacement, the self part of the intermediate scattering function, the diffusion coefficient and the α relaxation time. Finally, using one of the main results of the non-equilibrium self-consistent generalized Langevin equation theory (NE-SCGLE), we determine the dynamic arrest phase diagram in the volume fraction and temperature (φ vs T) plane.

Spatially heterogeneous dynamics and locally arrested density fluctuations from first principles

We present a first-principles formalism for studying dynamical heterogeneities in glass-forming liquids. Based on the non-equilibrium self-consistent generalized Langevin equation theory, we were able to describe the time-dependent local density profile during the particle interchange among small regions of the fluid. The final form of the diffusion equation contains both the contribution of the chemical potential gradient written in terms of a coarse-grained density and a collective diffusion coefficient as well as the effect of a history-dependent mobility factor. With this diffusion equation, we captured interesting phenomena in glass-forming liquids such as the cases when a strong density gradient is accompanied by a very low mobility factor attributable to the denser part: in such circumstances, the density profile falls into an arrested state even in the presence of a density gradient. On the other hand, we also show that above a certain critical temperature, which depends on the volume fraction, any density heterogeneity relaxes to a uniform state in a finite time, known as equilibration time. We further show that such equilibration time varies little with the temperature in diluted systems but can change drastically with temperature in concentrated systems.

Ultra-slow and arrested density-fluctuations as precursor of spatial heterogeneity

Dynamical heterogeneities in glass-forming liquids subjected to cooling processes are studied by a theoretical framework based on the non-equilibrium self-consistent generalized Langevin equation theory. This theory predicts that slow cooling rates permit the relaxation to the equilibrium state distinguished by a homogeneous local density. In contrast, fast cooling rates provoke dynamically arrested density-fluctuations and the establishment of permanent spatial heterogeneities even in the presence of density gradients. We further show that the dynamics toward the arrested state has two steps: a truncated relaxation followed by a second relaxation of the diluted part of the system.

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 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.

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.

Crossover from equilibration to aging: Nonequilibrium theory versus simulations.

Understanding glasses and the glass transition requires comprehending the nature of the crossover from the ergodic (or equilibrium) regime, in which the stationary properties of the system have no history dependence, to the mysterious glass transition region, where the measured properties are nonstationary and depend on the protocol of preparation. In this work we use nonequilibrium molecular dynamics simulations to test the main features of the crossover predicted by the molecular version of the recently developed multicomponent nonequilibrium self-consistent generalized Langevin equation theory. According to this theory, the glass transition involves the abrupt passage from the ordinary pattern of full equilibration to the aging scenario characteristic of glass-forming liquids. The same theory explains that this abrupt transition will always be observed as a blurred crossover due to the unavoidable finiteness of the time window of any experimental observation. We find that within their finite waiting-time window, the simulations confirm the general trends predicted by the theory.

Self-consistent generalized Langevin equation theory of the dynamics of multicomponent atomic liquids

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 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 a 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.

Communication: Probing the existence of partially arrested states in ionic liquids.

The recent predictions of the self-consistent generalized Langevin equation theory, describing the existence of unusual partially arrested states in the context of ionic liquids, were probed using all-atom molecular dynamics simulations of a room-temperature ionic liquid. We have found a slower diffusion of the smaller anions compared with the large cations for a wide range of temperatures. The arrest mechanism consists on the formation of a strongly repulsive glass by the anions, stabilized by the long range electrostatic potential. The diffusion of the less repulsive cations occurs through the holes left by the small particles. All of our observations in the simulated system coincide with the theoretical picture.

Equilibration and Aging of Liquids of Non-Spherically Interacting Particles.

The nonequilibrium self-consistent generalized Langevin equation theory of irreversible processes in liquids is extended to describe the positional and orientational thermal fluctuations of the instantaneous local concentration profile n(r,Ω,t) of a suddenly quenched colloidal liquid of particles interacting through nonspherically symmetric pairwise interactions, whose mean value n(r,Ω,t) is constrained to remain uniform and isotropic, n (r,Ω, t) = n (t). Such self-consistent theory is cast in terms of the time-evolution equation of the covariance [Formula: see text] of the fluctuations [Formula: see text] of the spherical harmonics projections nlm(k;t) of the Fourier transform of n(r,Ω,t). The resulting theory describes the nonequilibrium evolution after a sudden temperature quench of both, the static structure factor projections Slm(k,t) and the two-time correlation function [Formula: see text], where τ is the correlation delay time and t is the evolution or waiting time after the quench. As a concrete and illustrative application we use the resulting self-consistent equations to describe the irreversible processes of equilibration or aging of the orientational degrees of freedom of a system of strongly interacting classical dipoles with quenched positional disorder.

Non-equilibrium theory of arrested spinodal decomposition.

The non-equilibrium self-consistent generalized Langevin equation theory of irreversible relaxation [P. E. Ramŕez-González and M. Medina-Noyola, Phys. Rev. E 82, 061503 (2010); 82, 061504 (2010)] is applied to the description of the non-equilibrium processes involved in the spinodal decomposition of suddenly and deeply quenched simple liquids. For model liquids with hard-sphere plus attractive (Yukawa or square well) pair potential, the theory predicts that the spinodal curve, besides being the threshold of the thermodynamic stability of homogeneous states, is also the borderline between the regions of ergodic and non-ergodic homogeneous states. It also predicts that the high-density liquid-glass transition line, whose high-temperature limit corresponds to the well-known hard-sphere glass transition, at lower temperature intersects the spinodal curve and continues inside the spinodal region as a glass-glass transition line. Within the region bounded from below by this low-temperature glass-glass transition and from above by the spinodal dynamic arrest line, we can recognize two distinct domains with qualitatively different temperature dependence of various physical properties. We interpret these two domains as corresponding to full gas-liquid phase separation conditions and to the formation of physical gels by arrested spinodal decomposition. The resulting theoretical scenario is consistent with the corresponding experimental observations in a specific colloidal model system.

Non-equilibrium dynamics of glass-forming liquid mixtures

The non-equilibrium self-consistent generalized Langevin equation theory of irreversible processes in glass-forming liquids [P. Ramírez-González and M. Medina-Noyola, Phys. Rev. E 82, 061503 (2010)] is extended here to multi-component systems. The resulting theory describes the statistical properties of the instantaneous local particle concentration profiles nα(r, t) of species α in terms of the coupled time-evolution equations for the mean value n̄α(r, t) and for the covariance σ(αβ)(r, r'; t) ≡ δn(α)(r, t)δn(β)(r', t) of the fluctuations δn(α)(r, t) = n(α)(r, t) - n̄α(r, t). As in the monocomponent case, these two coarse-grained equations involve a local mobility function bα(r, t) for each species, written in terms of the memory function of the two-time correlation function C(αβ)(r, r'; t, t') ≡ δn(α)(r, t)δn(β)(r', t'). If the system is constrained to remain spatially uniform and subjected to a non-equilibrium preparation protocol described by a given temperature and composition change program T(t) and n̄α(r, t), these equations predict the irreversible structural relaxation of the partial static structure factors Sαβ(k; t) and of the (collective and self) intermediate scattering functions Fαβ(k, τ; t) and F(αβ)(S)(k, τ; t). We illustrate the applicability of the resulting theory with two examples involving simple model mixtures subjected to an instantaneous temperature quench: an electroneutral binary mixture of equally sized and oppositely charged hard-spheres, and a binary mixture of soft-spheres of moderate size-asymmetry.

Equilibration and aging of dense soft-sphere glass-forming liquids

The recently developed nonequilibrium extension of the self-consistent generalized Langevin equation theory of irreversible relaxation [Ramírez-González and Medina-Noyola, Phys. Rev. E 82, 061503 (2010); Ramírez-González and Medina-Noyola, Phys. Rev. E 82, 061504 (2010)] is applied to the description of the irreversible process of equilibration and aging of a glass-forming soft-sphere liquid that follows a sudden temperature quench, within the constraint that the local mean particle density remains uniform and constant. For these particular conditions, this theory describes the nonequilibrium evolution of the static structure factor S(k;t) and of the dynamic properties, such as the self-intermediate scattering function F(S)(k,τ;t), where τ is the correlation delay time and t is the evolution or waiting time after the quench. Specific predictions are presented for the deepest quench (to zero temperature). The predicted evolution of the α-relaxation time τ(α)(t) as a function of t allows us to define the equilibration time t(eq)(φ), as the time after which τ(α)(t) has attained its equilibrium value τ(α)(eq)(φ). It is predicted that both, t(eq)(φ) and τ(α)(eq)(φ), diverge as φ→φ((a)), where φ((a)) is the hard-sphere dynamic-arrest volume fraction φ((a))(≈0.582), thus suggesting that the measurement of equilibrium properties at and above φ((a)) is experimentally impossible. The theory also predicts that for fixed finite waiting times t, the plot of τ(α)(t;φ) as a function of φexhibits two regimes, corresponding to samples that have fully equilibrated within this waiting time (φ≤φ((c))(t)), and to samples for which equilibration is not yet complete (φ≥φ((c))(t)). The crossover volume fraction φ((c))(t) increases with t but saturates to the value φ((a)).

Aging of a homogeneously quenched colloidal glass-forming liquid

The nonequilibrium self-consistent generalized Langevin equation theory of colloid dynamics is used to describe the nonstationary aging processes occurring in a suddenly quenched model colloidal liquid with hard-sphere plus short-ranged attractive interactions, whose static structure factor and van Hove function evolve irreversibly from the initial conditions before the quench to a final dynamically arrested state. The comparison of our numerical results with available simulation data are highly encouraging.

Ionic and Wigner Glasses, Superionic Conductors, and Spinodal Electrostatic Gels: Dynamically Arrested Phases of the Primitive Model

Based on the recently proposed self-consistent generalized Langevin equation theory of dynamic arrest, in this letter we show that the ergodic-nonergodic phase diagram of a classical mixture of charged hard spheres (the so-called "primitive model" of ionic solutions and molten salts) includes arrested phases corresponding to nonconducting ionic glasses, partially arrested states that represent solid electrolytes (or "superionic" conductors), low-density colloidal Wigner glasses, and low-density electrostatic gels associated with arrested spinodal decomposition.

Alternative View of Dynamic Arrest in Colloid-Polymer Mixtures

Colloid-polymer mixtures are frequently viewed as an effective one-component fluid (the colloid) with polymer-mediated depletion interactions. This view, together with conventional mode coupling theory, constitutes the current description of the reentrant glass transition experimentally observed in these systems. A more fundamental view is to consider these systems as what they actually are, namely, genuine highly size-asymmetric binary colloidal mixtures. In this Letter we demonstrate that the recently developed multicomponent self-consistent generalized Langevin equation theory of dynamic arrest correctly predicts the observed reentrance in excellent quantitative agreement with the experimental glass transition line of a colloid-polymer mixture. In this scenario the polymer plays a much more active dynamic role than in the conventional one-component description.

Theory of dynamic arrest in colloidal mixtures

We present a first-principles theory of dynamic arrest in colloidal mixtures based on the multicomponent self-consistent generalized Langevin equation theory of colloid dynamics [M. A. Chávez-Rojo and M. Medina-Noyola, Phys. Rev. E 72, 031107 (2005); M. A. Chávez-Rojo and M. Medina-Noyola, Phys. Rev. E76, 039902 (2007)]. We illustrate its application with a description of dynamic arrest in two simple model colloidal mixtures: namely, hard-sphere and repulsive Yukawa binary mixtures. Our results include observation of the two patterns of dynamic arrest, one in which both species become simultaneously arrested and the other involving the sequential arrest of the two species. The latter case gives rise to mixed states in which one species is arrested while the other species remains mobile. We also derive the ("bifurcation" or fixed-point") equations for the nonergodic parameters of the system, which takes the surprisingly simple form of a system of coupled equations for the localization length of the particles of each species. The solution of this system of equations indicates unambiguously which species is arrested (finite localization length) and which species remains ergodic (infinite localization length). As a result, we are able to draw the entire ergodic-nonergodic phase diagram of the binary hard-sphere mixture.