We conduct a numerical study of the dynamical behavior of a system of three-dimensional crosses, particles that consist of three mutually perpendicular line segments rigidly joined at their midpoints. In an earlier study [W. van Ketel et al., Phys. Rev. Lett. 94, 135703 (2005)] we showed that this model has the structural properties of an ideal gas, yet the dynamical properties of a strong glass former. In the present paper we report an extensive study of the dynamical heterogeneities that appear in this system in the regime where glassy behavior sets in. On the one hand, we find that the propensity of a particle to diffuse is determined by the structure of its local environment. The local density around mobile particles is significantly less than the average density, but there is little clustering of mobile particles, and the clusters observed tend to be small. On the other hand, dynamical susceptibility results indicate that a large dynamical length scale develops even at moderate densities. This suggests that propensity and other mobility measures are an incomplete measure of dynamical length scales in this system.
We review the phenomena of dynamical heterogeneity in glass-forming systems and its description within replica and mean-field theories of the glass transition.
This is our reply to the comment by Sausset and Tarjus (arXiv:0802.1631) on our paper titled "Correlation between Dynamic Heterogeneity and Medium-Range Order in Two-Dimensional Glass-Forming Liquids" [Phys. Rev. Lett. Vol. 99, No. 21, 215701 (2007)].
We compare dynamical heterogeneities in equilibrated supercooled liquids and in the nonequilibrium glassy state within the framework of the random first order transition theory. Fluctuating mobility generation and transport in the glass are treated by numerically solving stochastic continuum equations for mobility and fictive temperature fields that arise from an extended mode coupling theory containing activated events. Fluctuating spatiotemporal structures in aging and rejuvenating glasses lead to dynamical heterogeneity in glasses with characteristics distinct from those found in the equili…
The existence of a generalized fluctuation-dissipation theorem observed in simulations and experiments performed in various glassy materials is related to the concepts of local equilibration and heterogeneity in space. Assuming the existence of a dynamic coherence length scale up to which the system is locally equilibrated, we extend previous generalizations of the FDT relating static to dynamic quantities to the physically relevant domain where asymptotic limits of large times and sizes are not reached. The formulation relies on a simple scaling argument and has thus not the character of a th…
Cryogenic rejuvenation in metallic glasses reported in Ketov et al 's experiment (Nature(2015)524,200) has attracted much attention, both in experiments and numerical studies. The atomic mechanism of rejuvenation has been conjectured to be related to the heterogeneity of the glassy state, but the quantitative evidence is still elusive. Here we use molecular dynamics simulations of a model metallic glass to investigate the heterogeneity in the local thermal expansion. We then combine the resulting spatial distribution of thermal expansion with a continuum mechanics calculation to infer the inte…
We report results of molecular dynamics simulations of a binary Lennard-Jones system at zero pressure in the undercooled liquid and glassy states. We first follow the evolution of diffusivity and dynamic heterogeneity with temperature and show their correlation. In a second step we follow the ageing of a quenched glass. As diffusivity decreases with ageing, heterogeneity increases. We conclude that the heterogeneity is a property of the inherent diffusion of the relaxed state. The variations with aging time can be explained by annealing of quenched defect structures. This annealing has the sam…
We study the growing time scales and length scales associated with dynamical slow down for a realistic glass former, using computer simulations. We perform finite size scaling to evaluate a length scale associated with dynamical heterogeneity which grows as temperature decreases. However, relaxation times which also grow with decreasing temperature, do not show the same kind of scaling behavior with system size as the dynamical heterogeneity, indicating that relaxation times are not solely determined by the length scale of dynamical heterogeneity. We show that relaxation times are instead dete…
We examine the relation between the free volume per particle and the variance of the particle position, equivalent to a local Debye-Waller (DW) factor for a 2D glass-forming alloy using molecular dynamics simulations. We find that the latter quantity exhibits significant spatial heterogeneity despite involving trajectories two orders of magnitude shorter than those typically used to measure such heterogeneities. We find that the free volume exhibits no significant spatial correlation with the local DW factor. We conclude that the spatial variation in local free volume is not the cause of the s…
We show the correlation between nanoscale structural heterogeneity and mechanical property and glass forming ability of Zr-based metallic glasses (MGs). Detailed parameters of medium range ordering (MRO) that constitutes the structural heterogeneity, including the type, size, and volume fraction of MRO domains determined using 4-dimensional scanning transmission electron microscopy, directly correlate with the ductility and glass forming ability of Zr-Cu-Co-Al MGs. Mesoscale deformation simulation incorporating the experimentally determined MRO confirms that the diverse types and sizes of MRO …
We introduce a new quantity to probe the glass transition. This quantity is a linear generalized compressibility which depends solely on the positions of the particles. We have performed a molecular dynamics simulation on a glass forming liquid consisting of a two component mixture of soft spheres in three dimensions. As the temperature is lowered, the generalized compressibility drops sharply at the glass transition. Our results are consistent with the kinetic view of the glass transition, but not with an underlying second order phase transition.
Statistical Gauge Theory of Structural Glasses: Equilibrium Scenarios and Glass-Forming Ability
IMET UB RAS（俄罗斯科学院乌拉尔分院金属物理研究所）；Ural Federal University（乌拉尔联邦大学）；HPPI（高温等离子体物理研究所）；N. L. Dukhov Research Institute of Automatics (VNIIA)（N.L.杜霍夫自动技术研究院）
We propose and numerically implement a local probe of the static self-induced heterogeneity characterizing glass-forming liquids. The method relies on the equilibrium statistics of the overlap between pairs of configurations measured in mesoscopic cavities with unconstrained boundaries. By systematically changing the location of the probed cavity, we directly detect spatial variations of the overlap fluctuations. We provide a detailed analysis of the statistics of a local estimate of the configurational entropy and we infer an estimate of the surface tension between amorphous states, ingredien…
We present molecular dynamics results for a two component, two-dimensional Lennard-Jones supercooled liquid near the glass transition. We find that the supercooled liquid is spatially heterogeneous and that there are long-lived clusters whose size distribution satisfies a scaling relation up to a cutoff. The similarity of several properties of the supercooled liquid to those of a mean-field glass-forming fluid near the spinodal suggests that the glass transition in the supercooled liquid is associated with an underlying thermodynamic instability.
We introduce a new disordered system, the Super-Potts model, which is a more frustrated version of the Potts glass. Its elementary degrees of freedom are variables that can take M values and are coupled via pair-wise interactions. Its exact solution on a completely connected lattice demonstrates that for large enough M it belongs to the class of mean-field systems solved by a one step replica symmetry breaking Ansatz. Numerical simulations by the parallel tempering technique show that in three dimensions it displays a phenomenological behaviour similar to the one of glass-forming liquids. The …
We construct the equations for the growth kinetics of an aging structural glass within mode-coupling theory through a non-stationary variant of the 3-density correlator defined in Phys. Rev. Lett. {\bf 97}, 195701 (2006). We solve a schematic form of the resulting equations to obtain the coarsening of the dynamic heterogeneity, characterized via the 3-point correlator $χ_3(t,t_w)$, as a function of waiting time $t_w$. For a quench into the glass, we find that $χ_3$ attains a peak value $\sim t_w^{0.5}$ at $t -t_w \sim t_w^{0.8}$, providing a theoretical basis for the numerical observations of …
Dynamic heterogeneity as one of the most important properties in supercooled liquids has been found for several decades. However, its structural origin remains open for many systems. Here, we propose a new structural parameter to characterize local atomic packing in metallic liquids. It is found that the new parameter in a simulated metallic glass-forming liquid is closely correlated with potential energy and atomic mobility. It also exhibits significant spatial heterogeneities and these structural fluctuations show close correlation with the spatial distribution of the long-time dynamic prope…
The effective potential formalism is applied to glass forming liquids, choosing a coupling potential such that the "order parameter", conjugated to the coupling strength, is the mean square displacement of the particles from their position in the quenched reference configuration. The potential is linear in some interval of its argument, signaling the coexistence of two phases in the system, one with low and one with high mean square displacement. Within this formalism, one can also compute the free energy of metastable states and their complexity.
We report nano-scale mechanical heterogeneity of a metallic glass characterized by dynamic atomic force microscopy. Apparent energy dissipation with the variation of ~12%, originating from non-uniform distribution of local viscoelasticity, was characterized. The correlation length of heterogeneous viscoelasticity was measured to be ~2.5{\pm}0.3 nm, which is well consistent with the dimension of shear transformation zones for plastic flow. This study provides the first experimental observation on the nano-scale mechanical heterogeneity in a metallic glass, and may fill the gap between atomic mo…
We show that a glass transition, signaled by a peak in the specific heat vs. temperature, can occur because a glassy system that shows no signs of aging progresses so slowly through the energy landscape that the time needed to obtain an accurate estimate of the thermodynamic averages exceeds the observation time. We find that below the glass transition temperature of a three dimensional binary mixture of soft spheres, the specific heat increases with measurement time spans orders of magnitude longer than previously recognized equilibration times.
We investigate a binary Lennard-Jones mixture with molecular dynamics simulations. We consider first a system cooled linearly in time with the cooling rate gamma. By varying gamma over almost four decades we study the influence of the cooling rate on the glass transition and on the resulting glass. We find for all investigated quantities a cooling rate dependence; with decreasing cooling rate the system falls out of equilibrium at decreasing temperatures, reaches lower enthalpies and obtains increasing local order. Next we study the dynamics of the melting process by investigating the most imm…
Dynamical heterogeneities -- strong fluctuations near the glass transition -- are believed to be crucial to explain much of the glass transition phenomenology. One possible hypothesis for their origin is that they emerge from soft (Goldstone) modes associated with a broken continuous symmetry under time reparametrizations. To test this hypothesis, we use numerical simulation data from four glass-forming models to construct coarse grained observables that probe the dynamical heterogeneity, and decompose the fluctuations of these observables into two transverse components associated with the pos…
We test a hypothesis for the origin of dynamical heterogeneity in slowly relaxing systems, namely that it emerges from soft (Goldstone) modes associated with a broken continuous symmetry under time reparametrizations. We do this by constructing coarse grained observables and decomposing the fluctuations of these observables into transverse components, which are associated with the postulated time-fluctuation soft modes, and a longitudinal component, which represents the rest of the fluctuations. Our test is performed on data obtained in simulations of four models of structural glasses. As the …
Using computer simulations of an atomistic glass-forming liquid, we investigate the fluctuations of the overlap between a fluid configuration and a quenched reference system. We find that large fluctuations of the overlap develop as temperature decreases, consistent with the existence of the random critical point that is predicted by effective field theories. We discuss the scaling of fluctuations near the presumed critical point, comparing the observed behaviour with that of the random-field Ising model. We argue that this critical point directly reveals the existence of an interfacial tensio…
The most puzzling aspect of the glass transition observed in laboratory is an apparent decoupling of dynamics from structure. In this paper we recount the implication of various theories of glass transition for the static correlation length in an attempt to reconcile the dynamic and static lengths associate with the glass problem. We argue that a more recent characterization of the static relaxation length based on the bond ordering scenario, as the typical length over which the energy fluctuations are correlated, is more consistent with, and indeed in perfect agreement with the typical linear…
A Monte Carlo method is used in order to simulate the competition between the molecular relaxation and crystallization times in the formation of a glass. The results show that nucleation is avoided during supercooling and produce self-organization in the sense of the rigidity theory, where the number of geometrical constraints due to bonding and excluded volume are compared with the degress of freedom available to the system. Following this idea, glass transitions were obtained by producing self-organization, and in the case of geometrical frustration, self-organization is naturally observed.
Thermal conductivity of a model glass-forming system in the liquid and glass states is studied using extensive numerical simulations. We show that near the glass transition temperture, where the structural relaxation time becomes very long, the measured thermal conductivity decreases with increasing age. Secondly the thermal conductivity of the disordered solid obtained at low temperatures depends on the cooling rate with which it was prepared, with lower cooling rates leading to lower thermal conductivity. Our analysis links this decrease of the thermal conductivity with increased exploration…
We demonstrate through two case studies, one on the p-spin interaction model and the other on the random K-satisfiability problem, that a heterogeneity transition occurs to the ground-state configuration space of a random finite-connectivity spin glass system at certain critical value of the constraint density. At the transition point, exponentially many configuration communities emerge from the ground-state configuration space, making the entropy density s(q) of configuration-pairs a non-concave function of configuration-pair overlap q. Each configuration community is a collection of relative…
A key property of glass forming alloys, the anomalously small volume difference with respect to the crystal, is shown to arise as a direct consequence of the soft repulsive potentials between metals. This feature of the inter-atomic potential is demonstrated to be responsible for a significant component of the glass forming ability of alloys due to the decrease in the enthalpy of fusion and the associated depression of the freezing point.
We report an investigation of the heterogeneity in super-cooled liquids and glasses using the non-Gaussianity parameter. We simulate selenium and a binary Lennard-Jones system by molecular dynamics. In the non-Gaussianity three time domains can be distinguished. First there is an increase on the ps-scale due to the vibrational (ballistic) motion of the atoms. This is followed, on an intermediate time-scale, by a growth, due to local relaxations (beta-relaxation) at not too high temperatures. A maximum is reached at times corresponding to long range diffusion (alpha-relaxation). At long times t…
We use large scale computer simulations of a glass-forming liquid in which a fraction c of the particles has been permanently pinned. We find that the relaxation dynamics shows an exponential dependence on c. This result can be rationalized by means of a simple theoretical Ansatz and we discuss its implication for thermodynamic theories for the glass-transition. For intermediate and low temperatures we find that the slowing down of the dynamics due to the pinning saturates and that the cooperativity decreases with increasing c, results which indicate that in glass-forming liquids there is a dy…
Dynamical heterogeneity and large deviations in the open quantum East glass model from tensor networks
University of Nottingham（诺丁汉大学）；Centre for the Mathematics and Theoretical Physics of Quantum Non-Equilibrium Systems, University of Nottingham（诺丁汉大学量子非平衡系统数学与理论物理中心）；Max-Planck-Institut für Quantenoptik（马克斯·普朗克量子光学研究所）；Munich Center for Quantum Science and Technology (MCQST)（慕尼黑量子科学与技术中心）
The behaviour of a model glass forming liquid is analyzed for a range of densities, with a focus on the temperature interval where the liquid begins to display non-Arrhenius temperature dependence of relaxation times. Analyzing the dynamics along with properties of local potential energy minima sampled by the liquid, a crossover or onset temperature $T_s$ is identified below which the liquid manifests {\it slow dynamics}, and a change in the character of typical local potential energy minima.
We study the local dynamical fluctuations in glass-forming models of particles embedded in $d$-dimensional space, in the mean-field limit of $d\to\infty$. Our analytical calculation reveals that single-particle observables, such as squared particle displacements, display divergent fluctuations around the dynamical (or mode-coupling) transition, due to the emergence of nontrivial correlations between displacements along different directions. This effect notably gives rise to a divergent non-Gaussian parameter, $α_2$. The $d\to\infty$ local dynamics therefore becomes quite rich upon approaching …
Recent experiments and computer simulations show that supercooled liquids around the glass transition temperature are "dynamically heterogeneous" [1]. Such heterogeneity is expected from the random first order transition theory of the glass transition. Using a microscopic approach based on this theory, we derive a relation between the departure from Debye relaxation as characterized by the $β$ value of a stretched exponential response function $ϕ(t) =e^{-(t/ τ_{KWW})^β}$, and the fragility of the liquid. The $β$ value is also predicted to depend on temperature and to vanish as the ideal glass …
The relationship between spatially heterogeneous dynamics (SHD) and jamming is studied in a glass-forming binary Lennard-Jones system via molecular dynamics simulations. It has been suggested that the probability distribution of interparticle forces $P(F)$ develops a peak at the glass transition temperature $T_g$, and that the large force inhomogeneities, responsible for structural arrest in granular materials, are related to dynamical heterogeneities in supercooled liquids that form glasses. It has been further suggested that ``force chains'' present in granular materials may exist in superco…
Glass-forming liquids display strong fluctuations -- dynamical heterogeneities -- near their glass transition. By numerically simulating a binary Weeks-Chandler-Andersen liquid and varying both temperature and timescale, we investigate the probability distributions of two kinds of local fluctuations in the non-equilibrium (aging) regime and in the equilibrium regime; and find them to be very similar in the two regimes and across temperatures. We also observe that, when appropriately rescaled, the integrated dynamic susceptibility is very weakly dependent on temperature and very similar in both…
We numerically study the zero-temperature relaxation dynamics of several glass-forming models to their inherent structures, following quenches from equilibrium configurations sampled across a wide range of initial temperatures. In a mean-field Mari-Kurchan model, we find that relaxation changes from a power-law to an exponential decay below a well-defined temperature, consistent with recent findings in mean-field $p$-spin models. By contrast, for finite-dimensional systems, the relaxation is always algebraic, with a non-trivial universal exponent at high temperatures crossing over to a harmoni…
Mixtures of glass-forming fluids sometimes exhibit glass-glass phase separation at low temperatures. Here, we use a molecular dynamics simulation to study one of the simplest examples of the glass-glass phase separation. We consider a mixture composed of type A and B particles, in which the A-A and B-B interactions are the identical Lennard-Jones interactions and the A-B interaction is repulsive only. To avoid crystallization, we also introduce the polydispersity in the particle sizes for each component. We study the phase separation kinetics of this model at a 50:50 concentration at various t…
The configurational entropy is one of the most important thermodynamic quantities characterizing supercooled liquids approaching the glass transition. Despite decades of experimental, theoretical, and computational investigation, a widely accepted definition of the configurational entropy is missing, its quantitative characterization remains fraud with difficulties, misconceptions and paradoxes, and its physical relevance is vividly debated. Motivated by recent computational progress, we offer a pedagogical perspective on the configurational entropy in glass-forming liquids. We first explain w…
The Shintani-Tanaka model is a glass-forming system whose constituents interact via anisotropic potential depending on the angle of a unit vector carried by each particle. The decay of time-correlation functions of the unit vectors exhibits the characteristics of generic relaxation functions during glass transitions. In particular it exhibits a 'stretched exponential' form, with the stretching index beta depending strongly on the temperature. We construct a quantitative theory of this correlation function by analyzing all the physical processes that contribute to it, separating a rotational fr…
In the context of a classical example of glass-formation in 3-dimensions we exemplify how to construct a statistical mechanical theory of the glass transition. At the heart of the approach is a simple criterion for verifying a proper choice of up-scaled quasi-species that allow the construction of a theory with a finite number of 'states'. Once constructed, the theory identifies a typical scale $ξ$ that increases rapidly with lowering the temperature and which determines the $α$-relaxation time $τ_α$ as $τ_α\sim \exp(μξ/T)$ with $μ$ a typical chemical potential. The theory can predict relaxati…
Dielectric spectroscopy is one of the most commonly used techniques for the investigation of the dynamic response of glass-forming materials. The tremendous slow-down of the particle motions when approaching the glass transition and especially the fast processes in glass-forming materials, which have come into the focus of scientific interest recently, make the investigation in a wide frequency range highly desirable. Recently, results from broadband dielectric spectroscopy on glass-forming materials in their liquid and supercooled-liquid state, covering more than 18 decades of frequency have …
In this note we apply some theoretical predictions that arise in the mean field framework for a large class of infinite range models to structural glasses and we present a first comparison of these predictions with numerical results.
Although several theories relate the steep slowdown of glass formers to increasing spatial correlations of some sort, standard static correlation functions show no evidence for this. We present results that reveal for the first time a qualitative thermodynamic difference between the high temperature and deeply supercooled equilibrium glass-forming liquid: the influence of boundary conditions propagates into the bulk over larger and larger lengthscales upon cooling, and, as this static correlation length grows, the influence decays nonexponentially. Increasingly long-range susceptibility to bou…
We propose that glass-forming liquids are intrinsically under the influences of both fluctuating interactions and random fields well-known in the field of spin systems. This is due to the frustration between the isotropic and anisotropic parts of effective intermolecular interactions. Our model indicates the existence of two key temperatures relevant to glass transition, the density ordering point T^*_m and the Vogel-Fulcher temperature T_0. Between T^*_m and T_0, a system has features similar to the `Griffiths phase', while below $T_0$ it has those peculiar to the `spin-glass phase'. This pic…
In this paper a simple model is proposed to decribe the spontaneous formation of coalitions among a group of actors like countries. The basic ingredients are from the physics of disorder systems. It is the interplay of two different spin glass models with respectively random bond and random site disorders which is instrumental in the present approach. The cold war stabilty period is then given an explanation as well the instabilities produced by the Warsow pact dissolution. European and Chinese stabilities are also discussed.
A large-scale molecular dynamics simulation is performed on a glass-forming Lennard-Jones mixture to determine the nature of dynamical heterogeneities which arise in this model fragile liquid. We observe that the most mobile particles exhibit a cooperative motion in the form of string-like paths (``strings'') whose mean length and radius of gyration increase as the liquid is cooled. The length distribution of the strings is found to be similar to that expected for the equilibrium polymerization of linear polymer chains.
If quenched fast enough, a liquid is able to avoid crystallization and will remain in a metastable supercooled state down to the glass transition, with an important increase in viscosity upon further cooling. There are important differences in the way liquids relax as they approach the glass transition, rapid or slow variation in dynamic quantities under moderate temperature changes, and a simple means to quantify such variations is provided by the concept of "fragility". Here, we report molecular dynamics simulations of a typical network-forming glass, Ge-Se, and find that the relaxation beha…
We discuss a novel approach, the point-to-set correlation functions, that allows to determine relevant static and dynamic length scales in glass-forming liquids. We find that static length scales increase monotonically when the temperature is lowered, whereas the measured dynamic length scale shows a maximum around the critical temperature of mode-coupling theory. We show that a similar non-monotonicity is found in the temperature evolution of certain finite size effects in the relaxation dynamics. These two independent sets of results demonstrate the existence of a change in the transport mec…
The fragility, that controls the temperature-dependent viscous properties of liquids as the glass transition is approached, in various glass-forming liquids with different atomic interactions and densities is investigated by molecular dynamic simulations. We show the landscape of fragility in purely repulsive systems can be separated into three regions with qualitatively disparate dynamic behaviors, suggesting that the density plays an unexpected role for understanding the repulsive steepness dependence of fragility. Furthermore, the vastly dissimilar influences of attractive interaction on fr…
