Model Glass-forming Liquid Research Articles

Selecting relevant structural features for glassy dynamics by information imbalance.

We numerically investigate the identification of relevant structural features that contribute to the dynamical heterogeneity in a model glass-forming liquid. By employing the recently proposed information imbalance technique, we select these features from a range of physically motivated descriptors. This selection process is performed in a supervised manner (using both dynamical and structural data) and an unsupervised manner (using only structural data). We then apply the selected features to predict future dynamics using a machine learning technique. One of the advantages of the information imbalance technique is that it does not assume any model a priori, i.e., it is a non-parametric method. Finally, we discuss the potential applications of this approach in identifying the dominant mechanisms governing the glassy slow dynamics.

Is the glassy dynamics same in 2D as in 3D? The Adam Gibbs relation test.

It has been recognized of late that even amorphous, glass-forming materials in two dimensions (2D) are affected by Mermin-Wagner-type long wavelength thermal fluctuation, which is inconsequential in three dimensions (3D). We consider the question of whether the effect of spatial dimension on dynamics is only limited to such fluctuations or if the nature of glassy dynamics is intrinsically different in 2D. To address it, we study the relationship between dynamics and thermodynamics using the Adam-Gibbs (AG) relation and the random first order transition (RFOT) theory. Using two model glass-forming liquids, we find that even after removing the effect of long wavelength fluctuations, the AG relation breaks down in two dimensions. Next, we consider the effect of anharmonicity of vibrational entropy-a second factor that affects the thermodynamics but not dynamics. Using the potential energy landscape formalism, we explicitly compute the configurational entropy, both with and without the anharmonic correction. We show that even with both the corrections, the AG relation still breaks down in 2D. The extent of deviation from the AG relation crucially depends on the attractive vs repulsive nature of interparticle interactions, choice of representative timescale (diffusion coefficient vs α-relaxation time), and implies that the RFOT scaling exponents also depend on these factors. Thus, our results suggest that some differences in the nature of glassy dynamics between 2D and 3D remain that are not explained by long wavelength fluctuations.

Universal origin of glassy relaxation as recognized by configuration pattern matching.

Relaxation processes are crucial for understanding the structural rearrangements of liquids and amorphous materials. However, the overarching principle that governs these processes across vastly different materials remains an open question. Substantial analysis has been carried out based on the motions of individual particles. Here, as an alternative, we propose viewing the global configuration as a single entity. We introduce a global order parameter, namely the inherent structure minimal displacement (IS Dmin), to quantify the variability of configurations by a pattern-matching technique. Through atomic simulations of seven model glass-forming liquids, we unify the influences of temperature, pressure and perturbation time on the relaxation dissipation, via a scaling law between the mechanical damping factor and IS Dmin. Fundamentally, this scaling reflects the curvature of the local potential energy landscape. Our findings uncover a universal origin of glassy relaxation and offer an alternative approach to studying disordered systems.

Soft pinning: Experimental validation of static correlations in supercooled molecular glass-forming liquids.

Enormous enhancement in the viscosity of a liquid near its glass transition is a hallmark of glass transition. Within a class of theoretical frameworks, it is connected to growing many-body static correlations near the transition, often called "amorphous ordering." At the same time, some theories do not invoke the existence of such a static length scale in the problem. Thus, proving the existence and possible estimation of the static length scales of amorphous order in different glass-forming liquids is very important to validate or falsify the predictions of these theories and unravel the true physics of glass formation. Experiments on molecular glass-forming liquids become pivotal in this scenario as the viscosity grows several folds (), and simulations or colloidal glass experiments fail to access these required long-time scales. Here we design an experiment to extract the static length scales in molecular liquids using dilute amounts of another large molecule as a pinning site. Results from dielectric relaxation experiments on supercooled Glycerol with different pinning concentrations of Sorbitol and Glucose, as well as the simulations on a few model glass-forming liquids with pinning sites, indicate the versatility of the proposed method, opening possible new avenues to study the physics of glass transition in other molecular liquids.

Statistical mechanics of coupled supercooled liquids in finite dimensions

We study the statistical mechanics of supercooled liquids when the system evolves at a temperature TT with a field \epsilonϵ linearly coupled to its overlap with a reference configuration of the same liquid sampled at a temperature T_0T0. We use mean-field theory to fully characterize the influence of the reference temperature T_0T0, and we mainly study the case of a fixed, low-T_0T0 value in computer simulations. We numerically investigate the extended phase diagram in the (\epsilon,T)(ϵ,T) plane of model glass-forming liquids in spatial dimensions d=2d=2 and d=3d=3, relying on umbrella sampling and reweighting techniques. For both 2d2d and 3d3d cases, a similar phenomenology with nontrivial thermodynamic fluctuations of the overlap is observed at low temperatures, but a detailed finite-size analysis reveals qualitatively distinct behaviors. We establish the existence of a first-order transition line for nonzero \epsilonϵ ending in a critical point in the universality class of the random-field Ising model (RFIM) in d=3d=3. In d=2d=2 instead, no phase transition is found in large enough systems at least down to temperatures below the extrapolated calorimetric glass transition temperature T_gTg. Our results confirm that glass-forming liquid samples of limited size display the thermodynamic fluctuations expected for finite systems undergoing a random first-order transition. They also support the relevance of the physics of the RFIM for supercooled liquids, which may then explain the qualitative difference between 2d2d and 3d3d glass-formers.

Spatial Dimensionality Dependence of Heterogeneity, Breakdown of the Stokes-Einstein Relation, and Fragility of a Model Glass-Forming Liquid.

We investigate the heterogeneity of dynamics, the breakdown of the Stokes-Einstein relation and fragility in a model glass forming liquid, a binary mixture of soft spheres with a harmonic interaction potential for spatial dimensions from 3 to 8. The dynamical heterogeneity is quantified through the dynamical susceptibility χ4 and the non-Gaussian parameter α2. We find that the fragility, the degree of breakdown of the Stokes-Einstein relation, and the heterogeneity of the dynamics decrease with increasing spatial dimensionality. We briefly describe the dependence of fragility on the density and use it to resolve an apparent inconsistency with previous results.

The microscopic origins of stretched exponential relaxation in two model glass-forming liquids as probed by simulations in the isoconfigurational ensemble.

The origin of stretched exponential relaxation in supercooled glass-forming liquids is one of the central questions regarding the anomalous dynamics of these fluids. The dominant explanation for this phenomenon has long been the proposition that spatial averaging over a heterogeneous distribution of locally exponential relaxation processes leads to stretching. Here, we perform simulations of model polymeric and small-molecule glass-formers in the isoconfigurational ensemble to show that stretching instead emerges from a combination of spatial averaging and locally nonexponential relaxation. The results indicate that localities in the fluid exhibiting faster-than-average relaxation tend to exhibit locally stretched relaxation, whereas slower-than-average relaxing domains exhibit more compressed relaxation. We show that local stretching is predicted by loose local caging, as measured by the Debye-Waller factor, and vice versa. This phenomenology in the local relaxation of in-equilibrium glasses parallels the dynamics of out of equilibrium under-dense and over-dense glasses, which likewise exhibit an asymmetry in their degree of stretching vs compression. On the basis of these results, we hypothesize that local stretching and compression in equilibrium glass-forming liquids results from evolution of particle mobilities over a single local relaxation time, with slower particles tending toward acceleration and vice versa. In addition to providing new insight into the origins of stretched relaxation, these results have implications for the interpretation of stretching exponents as measured via metrologies such as dielectric spectroscopy: measured stretching exponents cannot universally be interpreted as a direct measure of the breadth of an underlying distribution of relaxation times.

Time Scales of Fickian Diffusion and the Lifetime of Dynamic Heterogeneity

Dynamic heterogeneity, believed to be one of the hallmarks of the dynamics of supercooled liquids, is expected to affect the diffusion of the particles comprising the liquid. We have carried out extensive molecular dynamics simulations of two model glass-forming liquids in three dimensions to study the time scales at which Fick's law of diffusion starts to set in. We have identified two different Fickian times cales: one at which the mean squared displacement begins to show a linear dependence on time, and another one at which the distribution of particle displacements becomes Gaussian. These two times scales are found to be very different from each other and from the $\alpha$ relaxation time in both systems. An interesting connection is found between one of these Fickian time scales and the time scale obtained from the bond-breakage correlation function. We discuss the relation among these different times cales and their connection to dynamic heterogeneity in the system.

Signature of dynamical heterogeneity in spatial correlations of particle displacement and its temporal evolution in supercooled liquids

The existence of heterogeneity in the dynamics of supercooled liquids is believed to be one of the hallmarks of the glass transition. Intense research has been carried out in the past to understand the origin of this heterogeneity in dynamics and a possible length scale associated with it. We have done extensive molecular dynamics simulations of few model glass-forming liquids in three dimensions to understand the temporal evolution of the dynamic heterogeneity and the heterogeneity length scale. We find that although the strength of the dynamic heterogeneity is maximum at a timescale close to characteristic $\alpha$-relaxation time of the system, dynamic heterogeneity itself is well-developed at timescale as short as $\beta$-relaxation time and survives up to a timescale as long as few tens of $\alpha$-relaxation time. Moreover, we discovered that temperature dependence of heterogeneity length remains the same in the whole time window although its absolute value changes over time in a non-monotonic manner.

Role of Attractive Interactions in Structure Ordering and Dynamics of Glass-Forming Liquids

A key question in glass physics is what the origin of slow glassy dynamics is. The liquid structure is a natural candidate; however, an apparently severe counterexample has been known. Two model glass-forming liquids, with the standard Lennard-Jones interaction potential and its Weeks-Chandler-Andersen variation without the attractive tail, exhibit very similar structures at the two-body level but drastically different dynamical behaviors in the supercooled states. Here we look at the liquid structure through a (many-body) structural order parameter Θ characterizing the packing capability of local particle arrangements. We show that the structures of these two systems seen by Θ are actually very different at a many-body level, but, quite surprisingly, the macroscopic structure (Θ)-dynamics (τ_{α}) relationships commonly follow a Vogel-Fulcher-Tammann-like function. Furthermore, the mutual information analysis reveals strong local structure-dynamics correlations. Therefore, we conclude that attractive interactions affect the liquid structure in a nonperturbative manner, but a general structural origin of slow dynamics holds for these systems.

The influence of the nanocurvature on the surface interactions and molecular dynamics of model liquid confined in cylindrical pores

Currently, a great effort is put on the understanding of the effect of the nanometrical constraint on the dynamics of the soft materials. Recent studies by Alexandris et al. [Macromolecules,2016, 49, 7400–7414] and some of us [J. Phys. Chem. C, 2019,123, 5549–5556] revealed that the enhancement of the molecular mobility and depression in the glass transition of various low and high molecular weight glass formers infiltrated into Anodic Aluminum Oxide (AAO) templates strongly correlates with the strength of the interfacial interactions between the materials and the porous medium. However, in those investigations, one very important and fundamental aspect related to the variation in the wettability, the surface tension as well as the interfacial energy due to surface curvature has been completely overlooked. Herein, we have performed systematic and unique Atomic Force Microscopy (AFM) measurements on the model glass-forming liquid, glycerol (GLY), incorporated into porous AAO membranes of varying pore diameter. It was found that with increasing degree of confinement, the adhesion force between GLY and AFM tip decreases significantly. It seems that as indicated by the Tolman relation, the interfacial tension of the confined GLY drops leading to a better wetting of polyalcohol within the smallest pores. Interestingly, for this particular system (confined within templates of d = 10 nm), a complementary Differential Scanning Calorimetry (DSC) investigations revealed the presence of the two glass transition temperatures upon heating runs. This indicated that the enhancement of the interactions between alumina and alcohol leads to the formation of the interfacial layer that vitrifies at higher temperature (Tg,interfacial) than the bulk material. Interestingly, the observed double Tgs appeared only on heating. Moreover, different thermal protocols revealed the variation of the heat capacity jump corresponding to the glass transition temperature of the interfacial layer upon the annealing experiments, indicating the ongoing desorption process. In addition, it was also found that the structural dynamics of GLY incorporated within d = 10 nm starts to deviate below Tg,interfacial from the behavior of the non-confined sample. Reported data are the first experimental evidence on the correlation between variation of the surface interactions with the substrate's curvature and enhancement of the dynamics of the confined liquids. Thus, a better understanding of the dynamics of confined soft matter, especially the relation between the finite size and surface interactions can be gained.

Relaxation dynamics in supercooled oligomer liquids: From shear-stress fluctuations to shear modulus and structural correlations

Static and dynamical properties of a model glass-forming oligomer liquid are analyzed using molecular dynamics simulations. The temperature and system size effects are assessed for the affine shear modulus μA, the quasistatic shear modulus μsf (obtained using the stress-fluctuation relation), and the shear relaxation modulus G(t). It is found that while both μA and μsf are nearly independent of the system size, their variances show significant system size dependence, in particular, below the glass transition temperature Tg. It is also shown that the standard deviation of the shear modulus, δμsf(T), exhibits a pronounced peak at T ≈ Tg whose position is nearly independent of the system volume V. Moreover, the whole function δμsf(T) is nearly the same for different system sizes above the glass transition. We propose a theory which quantitatively predicts δμsf(T) at T ≳ Tg and explains both its independence of V and its peak near Tg. It is also established that below Tg the variance of the affine modulus follows the standard power law, δμA2∝1/V, while δμsf shows anomalously a slow decrease with V as δμsf2∝1/Vα with α < 1. On this basis, it is argued that the studied glass-forming systems must show long-range structural correlations in the amorphous state.

Revealing the Link between Structural Relaxation and Dynamic Heterogeneity in Glass-Forming Liquids.

Despite the use of glasses for thousands of years, the nature of the glass transition is still mysterious. On approaching the glass transition, the growth of dynamic heterogeneity has long been thought to play a key role in explaining the abrupt slowdown of structural relaxation. However, it still remains elusive whether there is an underlying link between structural relaxation and dynamic heterogeneity. Here, we unravel the link by introducing a characteristic time scale hiding behind an identical dynamic heterogeneity for various model glass-forming liquids. We find that the time scale corresponds to the kinetic fragility of liquids. Moreover, it leads to scaling collapse of both the structural relaxation time and dynamic heterogeneity for all liquids studied, together with a characteristic temperature associated with the same dynamic heterogeneity. Our findings imply that studying the glass transition from the viewpoint of dynamic heterogeneity is more informative than expected.

Energy Renormalization for Coarse-Graining the Dynamics of a Model Glass-Forming Liquid.

Coarse-grained modeling achieves the enhanced computational efficiency required to model glass-forming materials by integrating out "unessential" molecular degrees of freedom, but no effective temperature transferable coarse-graining method currently exists to capture dynamics. We address this fundamental problem through an energy-renormalization scheme, in conjunction with the localization model of relaxation relating the Debye-Waller factor ⟨u2⟩ to the structural relaxation time τ. Taking ortho-terphenyl as a model small-molecule glass-forming liquid, we show that preserving ⟨u2⟩ (at picosecond time scale) under coarse-graining by renormalizing the cohesive interaction strength allows for quantitative prediction of both short- and long-time dynamics covering the entire temperature range of glass formation. Our findings provide physical insights into the dynamics of cooled liquids and make progress for building temperature-transferable coarse-grained models that predict key properties of glass-forming materials.

From Glass Formation to Icosahedral Ordering by Curving Three-Dimensional Space.

Geometric frustration describes the inability of a local molecular arrangement, such as icosahedra found in metallic glasses and in model atomic glass formers, to tile space. Local icosahedral order, however, is strongly frustrated in Euclidean space, which obscures any causal relationship with the observed dynamical slowdown. Here we relieve frustration in a model glass-forming liquid by curving three-dimensional space onto the surface of a 4-dimensional hypersphere. For sufficient curvature, frustration vanishes and the liquid "freezes" in a fully icosahedral structure via a sharp "transition." Frustration increases upon reducing the curvature, and the transition to the icosahedral state smoothens while glassy dynamics emerge. Decreasing the curvature leads to decoupling between dynamical and structural length scales and the decrease of kinetic fragility. This sheds light on the observed glass-forming behavior in Euclidean space.

Exploring the Crystallization Tendency of Glass-Forming Liquid Indomethacin in the T–p Plane by Finding Different Iso-Invariant Points

In this work, we examine in detail the crystallization tendency of the model glass-forming liquid indomethacin at varying thermodynamic conditions. To do that, we combine experimental results with predictions of the classical theories of nucleation and growth. We have considered changes in the crystallization rate k along iso-invariant curves located differently in the T–p phase diagram of the studied supercooled liquid. We include for the first time temperature and pressure conditions along which the thermodynamic driving force toward crystallization, commonly discussed as the difference in the chemical potential of the liquid/crystalline phases, Δμ, is expected to remain constant. Although the increase in pressure fosters crystallization (due to an increasing overlap of the nucleation and growth rates maxima), we show that when moving along certain thermodynamic paths the crystallization rate remains unchanged, or it is only slightly affected by the density increase. Therefore, by studying the kinetics ...

An Overview on Short and Long Time Relaxations in Glass-forming Supercooled Liquids

Density fluctuations in supercooled liquids near the glass transition relax in multiple steps. The short time relaxation is known as β-relaxation and the final long time relaxation is called α-relaxation. It is believed that the long time α-relaxation is a cooperative phenomena associated with a growing length scales, whereas the short-time β-relaxation is often attributed to spatially local processes involving the rattling motion of a particle in the transient cage formed by its neighbors. Using molecular dynamics simulations of few model glass-forming liquids, we show that the β-relaxation is also cooperative in nature and the length scale extracted from the detailed finite-size scaling analysis of β-relaxation is found to be the same as that of the length scale that describes the spatial heterogeneity of local dynamics in the long-time α-relaxation regime. These results provide a clear connection between short-time dynamics and long-time structural relaxation in glass-forming liquids.

Understanding the dynamics of glass-forming liquids with random pinning within the random first order transition theory.

Extensive computer simulations are performed for a few model glass-forming liquids in both two and three dimensions to study their dynamics when a randomly chosen fraction of particles are frozen in their equilibrium positions. For all the studied systems, we find that the temperature-dependence of the α relaxation time extracted from an overlap function related to the self-part of the density autocorrelation function can be explained within the framework of the Random First Order Transition (RFOT) theory of the glass transition. We propose a scaling description to rationalize the simulation results and show that our data for the α relaxation time for all temperatures and pin concentrations are consistent with this description. We find that the fragility parameter obtained from fits of the temperature dependence of the α relaxation time to the Vogel-Fulcher-Tammann form decreases by almost an order of magnitude as the pin concentration is increased from zero. Our scaling description relates the fragility parameter to the static length scale of RFOT and thus provides a physical understanding of fragility within the framework of the RFOT theory. Implications of these findings for the values of the exponents appearing in the RFOT theory are discussed.

Short-Time Beta Relaxation in Glass-Forming Liquids Is Cooperative in Nature.

Temporal relaxation of density fluctuations in supercooled liquids near the glass transition occurs in multiple steps. Using molecular dynamics simulations for three model glass-forming liquids, we show that the short-time β relaxation is cooperative in nature. Using finite-size scaling analysis, we extract a growing length scale associated with beta relaxation from the observed dependence of the beta relaxation time on the system size. We find, in qualitative agreement with the prediction of the inhomogeneous mode coupling theory, that the temperature dependence of this length scale is the same as that of the length scale that describes the spatial heterogeneity of local dynamics in the long-time α-relaxation regime.

Negative Pressure Vitrification of the Isochorically Confined Liquid in Nanopores.

Dielectric relaxation studies for model glass-forming liquids confined to nanoporous alumina matrices were examined together with high-pressure results. For confined liquids which show the deviation from bulk dynamics upon approaching the glass transition (the change from the Vogel-Fulcher-Tammann to the Arrhenius law), we have observed a striking agreement between the temperature dependence of the α-relaxation time in the Arrhenius-like region and the isochoric relaxation times extrapolated from the positive range of pressure to the negative pressure domain. Our finding provides strong evidence that glass-forming liquid confined to native nanopores enters the isochoric conditions once the mobility of the interfacial layer becomes frozen in. This results in the negative pressure effects on cooling. We also demonstrate that differences in the sensitivity of various glass-forming liquids to the "confinement effects" can be rationalized by considering the relative importance of thermal energy and density contributions in controlling the α-relaxation dynamics (the E(v)/E(p) ratio).