We investigate the characteristic length scales associated with the glass transition phenomenon. By studying an atomic glass-forming liquid in negatively curved space, for which the local order is well identified and the amount of frustration opposing the spatial extension of this order is tunable, we provide insight into the structural origin of the main characteristics of the dynamics leading to glass formation. We find that the structural length and the correlation length characterizing the increasing heterogeneity of the dynamics grow together as temperature decreases. However, the system eventually enters a regime in which the former saturates as a result of frustration whereas dynamic correlations keep building up.
A low temperature Monte Carlo dynamics of a Keating like oscillator model is used to study the relationship between the nature of glasses from the viewpoint of rigidity, and the strong-fragile behaviour of glass-forming liquids. The model shows that a Phillips optimal glass formation with minimal enthalpic changes is obtained under a cooling/annealing cycle when the system is optimally constrained by the harmonic interactions, i.e. when it is isostatically rigid. For these peculiar systems, the computed fragility shows also a minimum, which demonstrates that isostatically rigid glasses are str…
The inherent structure approach, wherein thermodynamic and structural changes in glass forming liquids are analyzed in terms of local potential energy minima that the liquid samples, has recently been applied extensively to the study of thermodynamic aspects of glass forming liquids. The evalation of the configurational entropy, which arises from the multiplicity of local energy minima, plays a central role in such analyses. Results are presented here concerning the calculation of configurational entropy based on computer simulations of a model liquid, and the application of the inherent struc…
We show by means of a Monte Carlo simulation study that three-dimensional models with long-range frustration display the generic phenomena seen in fragile glassforming liquids. Due to their properties (absence of quenched disorder, physical motivation in terms of structural frustration, and tunable fragility), these systems appear as promising minimal theoretical models for describing the glass transition of supercooled liquids.
We analyse numerically thermal fluctuations of the static overlap between equilibrium configurations in a glass-forming liquid approaching the glass transition. We find that the emergence of slow dynamics near the onset temperature correlates with the development of non-Gaussian probability distributions of overlap fluctuations, measured using both annealed and quenched definitions. Below a critical temperature, a thermodynamic field conjugate to the overlap induces a first-order phase transition, whose existence we numerically demonstrate in the annealed case. These results establish that the…
We show how dynamical heterogeneities in glass forming systems emerge as a consequence of the existence of dynamical constraints, and we offer an interpretation of the glass transition as an entropy crisis in trajectory space (space-time) rather than in configuration space. To illustrate our general ideas, we analyze the one dimensional (d=1) Fredrickson-Andersen and East models. Dynamics of such dynamically constrained systems are shown to be isomorphic to the statics of d+1 dimensional dense mixtures of polydisperse non-interpenetrating domains. The domains coincide with arrested regions in …
We study by molecular dynamics computer simulation a binary soft-sphere mixture that shows a pronounced decoupling of the species' long-time dynamics. Anomalous, power-law-like diffusion of small particles arises, that can be understood as a precursor of a double-transition scenario, combining a glass transition and a separate small-particle localization transition. Switching off small-particle excluded-volume constraints slows down, rather than enhances, small-particle transport. The data are contrasted with results from the mode-coupling theory of the glass transition.
A comprehensive microscopic dynamical theory is presented for the description of quantum fluids as they transform into glasses. The theory is based on a quantum extension of mode-coupling theory. Novel effects are predicted, such as reentrant behavior of dynamical relaxation times. These predictions are supported by path integral ring polymer molecular dynamics simulations. The simulations provide detailed insight into the factors that govern slow dynamics in glassy quantum fluids. Connection to other recent work on both quantum glasses as well as quantum optimization problems is presented.
We present a calculation of a fourth-order, time-dependent density correlation function that measures higher-order spatiotemporall correlations of the density of a liquid. From molecular dynamics simulations of a glass-forming Lennard-Jones liquid, we find that the characteristic length scale of this function has a maximum as a function of time which increases steadily beyond the characteristic length of the static pair correlation function $g(r)$ in the temperature range approaching the mode coupling temperature from above.
In a recent letter, Kawasaki et al. (PRL 99, 215701 (2007)) study glass formation in a 2-dimensional (2D) model of polydisperse repulsive disks. They give numerical evidence for a direct relation between slowing down of the relaxation, extension of some medium-range order, and development of dynamic heterogeneities. We disagree with the authors' interpretation on two points which we believe to be potentially important for understanding the glass transition.
Characterization of the non-Arrhenius behavior of glass-forming liquids is a broad avenue for research toward the understanding of the formation mechanisms of noncrystalline materials. In this context, this paper explores the main properties of the viscosity of glass-forming systems, considering super-Arrhenius diffusive processes. We establish the viscous activation energy as a function of the temperature, measure the degree of fragility of the system, and characterize the fragile-to-strong transition through the standard Angell's plot. Our results show that the non-Arrhenius behavior observe…
A master equation description of the inherent dynamics is used to calculate the frequency-dependent linear thermo-visco-elastic response functions of a glass-forming liquid. From the imaginary parts of the isobaric specific heat, isothermal bulk modulus, and isobaric thermal expansion coefficient, we define a quantity $Λ_{Tp}(ω)$ with the property that $Λ_{Tp}(ω)=1$ is equivalent to having a one-parameter description of the linear thermo-visco-elastic response. This provides an alternative to the well-known criterion based on the Prigogine-Defay ratio.
We calculated a four-point correlation function G_4(k,r;t) and the corresponding structure factor S_4(k,q;t) for a model glass-forming binary mixture. These functions measure the spatial correlations of the relaxation of different particles. We found that these four-point functions are anisotropic and depend on the angle between vectors k and r (or q). The anisotropy is the strongest for times somewhat longer than the beta relaxation time but it is quite pronounced even for times comparable to the alpha relaxation time, tau_alpha. At the lowest temperatures S_4(k,q;tau_alpha) is strongly aniso…
We analyze static point-to-set correlations in glass-forming liquids. The generic idea is to freeze the position of a set of particles in an equilibrium configuration and to perform sampling in the presence of this additional constraint. Qualitatively different geometries for the confining set of particles are considered and a detailed comparison of resulting static and dynamic correlation functions is performed. Our results reveal the existence of static spatial correlations not detected by conventional two-body correlators, which appear to be decoupled from, and shorter-ranged than, dynamica…
In a preceding paper, Mukhopadhyay and I studied the diffusive motion of a tagged molecule in a heterogeneous glass-forming liquid at temperatures just above a glass transition. Among other features of this system, we postulated a relation between heterogeneity and stretched-exponential decay of correlations, and we also confirmed that systems of this kind generally exhibit non-Gaussian diffusion on intermediate length and time scales. Here I extend this analysis to higher temperatures approaching the point where the heterogeneities disappear and thermal activation barriers become small. I sta…
We review the phenomena of dynamical heterogeneity in glass-forming systems and its description within replica and mean-field theories of the glass transition.
A key open question in the glass transition field is whether a finite temperature thermodynamic transition to the glass state exists or not. Recent simulations of coupled replicas in atomistic models have found signatures of a static transition as a function of replica coupling. This can be viewed as evidence of an associated thermodynamic glass transition in the uncoupled system. We demonstrate here that a different interpretation is possible. We consider the triangular plaquette model, an interacting spin system which displays (East model-like) glassy dynamics in the absence of any static tr…
We use a standard Monte-Carlo algorithm to study the slow dynamics of a binary Lennard-Jones glass-forming mixture at low temperature. We find that Monte-Carlo is by far the most efficient way to simulate a stochastic dynamics since relaxation is about 10 times faster than in Brownian Dynamics and about 30 times faster than in Stochastic Dynamics. Moreover, the average dynamical behaviour of the system is in quantitative agreement with the one obtained using Newtonian dynamics, apart at very short times where thermal vibrations are suppressed. We show, however, that dynamic fluctuations quanti…
We assess the validity of "microscopic" approaches of glass-forming liquids based on the sole k nowledge of the static pair density correlations. To do so we apply them to a benchmark provided by two liquid models that share very similar static pair density correlation functions while disp laying distinct temperature evolutions of their relaxation times. We find that the approaches are unsuccessful in describing the difference in the dynamical behavior of the two models. Our study is not exhausti ve, and we have not tested the effect of adding corrections by including for instance three-body d…
Enormous enhancement in the viscosity of a liquid near its glass transition is generally connected to the growing many-body static correlations near the transition, often coined as `amorphous ordering'. Estimating the length scales of such correlations in different glass-forming liquids is highly important to unravel the physics of glass formation. Experiments on molecular glass-forming liquids become pivotal in this scenario as the viscosity grows several folds ($\sim 10^{14}$), simulations or colloidal glass experiments fail to access the long-time scales required. Here we design an experime…
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）
The term "fragility" describes the rate at which viscosity grows when a supercooled liquid approaches its putative glass transition temperature. The field of glassy materials is actively searching for a structural origin that governs this dynamical slowing down in the supercooled liquid, which occurs without any discernible change in structure. Our work shows clear evidence that growing many-body static amorphous order is intimately correlated with the kinetic fragility of glass-forming liquids. It confirms that the system's dynamical response to temperature is concealed in its micro-structure…
Understanding glass formation is a challenge because the existence of a true glass state, distinct from liquid and solid, remains elusive: Glasses are liquids that have become too viscous to flow. An old idea, as yet unproven experimentally, is that the dynamics becomes sluggish as the glass transition approaches because increasingly larger regions of the material have to move simultaneously to allow flow. We introduce new multipoint dynamical susceptibilities to estimate quantitatively the size of these regions and provide direct experimental evidence that the glass formation of molecular liq…
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 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.
The excess heat capacity at glass transition temperature in two types of glass-forming systems of [xNaNO3\cdot(1-x)KNO3]60[Ca(NO3)2]40 (0 \leq x \leq 1) and Ca(NO3)2\cdotyH2O (4 \leq y \leq 13) is studied. In the former system, with the replacement of K+ cation with Na+ cation, the excess heat capacity is almost invariable around 65.1 J\cdotmol-1\cdotK-1, while the excess increases by 38.9 J\cdotmol-1\cdotK-1 with the increasing per molar H2O content in latter system. A quantitative description of the excess heat capacity is built up with the consideration of atomic and molecular translational…
The memory kernel of the self-part of the intermediate scattering function is studied. We found that the short-time behavior of the memory kernel for our MD-simulated glass-forming Ni$_{20}$Zr$_{80}$-system shows a deviation from the polynomial form predicted by MCT. By using the gaussian approximation we give a more detailed description of the short-time dynamics of the system.
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 …
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.
Two versions of the M-p-spin glass model have been studied with the Migdal-Kadanoff renormalization group approximation. The model with p=3 and M=3 has at mean-field level the ideal glass transition at the Kauzmann temperature and at lower temperatures still the Gardner transition to a state like that of an Ising spin glass in a field. The model with p=3 and M=2 has only the Gardner transition. In the dimensions studied, d=2,3 and 4, both models behave almost identically, indicating that the growing correlation length as the temperature is reduced in these models -- the analogue of the point-t…
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 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 introduce simple models, inspired by previous models for froths and covalent glasses, with trivial equilibrium properties but dynamical behaviour characteristic of strong glass forming systems. These models are also a generalization of backgammon or urn models to a non--constant number of particles, where entropic barriers are replaced by energy barriers, allowing for the existence of activated processes. We formulate a mean--field version of the models, which keeps most of the features of the finite dimensional ones, and solve analytically the out--of--equilibrium dynamics in the low tempe…
This article discusses recent attempts to provide a deeper understanding of the thermoreversible "gel" state of colloidal matter and to unravel the analogies between gels at the colloidal level and gels at the molecular level, commonly known as network-forming strong liquids. The connection between gel-forming patchy colloids and strong liquids is provided by the limited valence of the inter-particle interactions, i.e. by the presence of a limit in the number of bonded nearest neighbors.
Understanding the mechanical properties of glasses remains elusive since the glass transition itself is not fully understood, even in well studied examples of glass formers in two dimensions. In this context we demonstrate here: (i) a direct evidence for a diverging length scale at the glass transition (ii) an identification of the glass transition with the disappearance of fluid-like regions and (iii) the appearance in the glass state of fluid-like regions when mechanical strain is applied. These fluid-like regions are associated with the onset of plasticity in the amorphous solid. The relaxa…
We study the four-point dynamic susceptibility $χ_4(t)$ obtained from Brownian dynamics computer simulations of the Kob-Andersen Lennard-Jones mixture. We compare the results of the simulations with qualitative predictions of the mode-coupling theory. In addition, we test an estimate of the four-point susceptibility recently proposed by Berthier \textit{et al.} [Science, \textbf{310}, 1797 (2005)].
We use the ``isoconfigurational ensemble'' [Phys. Rev. Lett. {\bf 93}, 135701 (2004)] to analyze both dynamical and structural properties in simulations of a glass forming molecular liquid. We show that spatially correlated clusters of low potential energy molecules are observable on the time scale of structural relaxation, despite the absence of spatial correlations of potential energy in the instantaneous structure of the system. We find that these structural heterogeneities correlate with dynamical heterogeneities in the form of clusters of low molecular mobility.
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…
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…
We identify a link between the glass transition and percolation of mobile regions in configuration space. We find that many hallmarks of glassy dynamics, for example stretched-exponential response functions and a diverging structural relaxation time, are consequences of the critical properties of mean-field percolation. Specific predictions of the percolation model include the range of possible stretching exponents $1/3 \leq β\leq 1$ and the functional dependence of the structural relaxation time $τ_α$ and exponent $β$ on temperature, density, and wave number.
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 present new simulation results for the specific heat in a classical model of a binary mixture glass-former in two dimensions. We show that in addition to the formerly observed specific heat peak there is a second peak at lower temperatures which was not observable in earlier simulations. This is a surprise, as most texts on the glass transition expect a single specific heat peak. We explain the physics of the two specific heat peaks by the micro-melting of two types of clusters. While this physics is easily accessible, the consequences are that one should not expect any universality in the …
All liquids are topologically disordered materials; however, the degree of disorder can vary as a result of internal fluctuations in structure and topology. These fluctuations depend on both the composition and temperature of the system. Most prior work has considered the mean values of liquid or glass properties, such as the average number of topological degrees of freedom per atom; however, the localized fluctuations in properties also play a key role in governing the macroscopic characteristics of any glass-forming system. This paper proposes a generalized approach for modeling topological …
We introduce a new theoretical model of simple fluid, whose interactions, defined in terms of the Voronoi cells of the configurations, are local and many-body. The resulting system is studied both theoretically and numerically. We show that the fluid, though sharing the global features of other models of fluids with soft interactions, has several unusual characteristics, which are investigated and discussed.
We introduce the ideal Gaussian glass-forming system as a model to describe the thermodynamics and dynamics of supercooled liquids on a local scale in terms of the properties of the potential energy landscape (PEL). The first ingredient is the Gaussian distribution of inherent structures, the second a specific relation between energy and mobility. This model is compatible with general considerations as well as with several computer simulations on atomic computer glass-formers. Important observables such as diffusion constants, structural relaxation times and kinetic as well as thermodynamic fr…
Temporal relaxation of density fluctuations in supercooled liquids near the glass transition occurs in multiple steps. The short-time $β$-relaxation is generally attributed to spatially local processes involving the rattling motion of a particle in the transient cage formed by its neighbors. Using molecular dynamics simulations for three model glass-forming liquids, we show that the $β$-relaxation is actually cooperative in nature. Using finite-size scaling analysis, we extract a growing length-scale associated with $β$-relaxation from the observed dependence of the $β$-relaxation time on the …
If a liquid is cooled rapidly to form a glass, its structural relaxation becomes retarded, producing a drastic increase in viscosity. In two dimensions, strong long-wavelength fluctuations persist, even at low temperature, making it difficult to evaluate the microscopic structural relaxation time. This Letter shows that, in a 2D glass-forming liquid, relative displacement between neighbor particles yields a relaxation time that grows in proportion to the viscosity. In addition to thermal elastic vibrations, hydrodynamic fluctuations are found to affect the long-wavelength dynamics, yielding a …
Translational dynamics of two-dimensional glass forming fluids is strongly influenced by soft, long-wavelength fluctuations first recognized by D. Mermin and H. Wagner. As a result of these fluctuations, characteristic features of glassy dynamics, such as plateaus in the mean squared displacement and the self-intermediate scattering function, are absent in two dimensions. In contrast, Mermin-Wagner fluctuations do not influence orientational relaxation and well developed plateaus are observed in orientational correlation functions. It has been suggested that by monitoring translational motion …
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 develop a minimal model to describe growing dense active matter such as biological tissues, bacterial colonies and biofilms, that are driven by a competition between particle division and steric repulsion. We provide a detailed numerical analysis of collective and single particle dynamics. We show that the microscopic dynamics can be understood as the superposition of an affine radial component due to the global growth, and of a more complex non-affine component which displays features typical of driven soft glassy materials, such as aging, compressed exponential decay of time correlation f…
We propose that the dynamics of supercooled liquids and the formation of glasses can be understood from the existence of a zero temperature dynamical critical point. To support our proposal, we derive from simple physical assumptions a dynamic field theory for supercooled liquids, which we study using the renormalization group (RG). Its long time behaviour is dominated by a zero temperature critical point, which for dimensions d > 2 belongs to the directed percolation universality class. Molecular dynamics simulations confirm the existence of dynamic scaling behaviour consistent with the RG pr…
We propose a simple theory for the dynamics of model glass-forming fluids, which should be solvable using a mean-field-like approach. The theory is based on transparent physical assumptions, which can be tested in computer simulations. The theory predicts an ergodicity-breaking transition that is identical to the so-called dynamic transition predicted within the replica approach. Thus, it can provide the missing dynamic component of the random first order transition framework. In the large-dimensional limit the theory reproduces the result of a recent exact calculation of Maimbourg et al. [PRL…
We address the interesting temperature range of a glass forming system where the mechanical properties are intermediate between those of a liquid and a solid. We employ an efficient Monte-Carlo method to calculate the elastic moduli, and show that in this range of temperatures the moduli are finite for short times and vanish for long times, where `short' and `long' depend on the temperature. By invoking some exact results from statistical mechanics we offer an alternative method to compute shear moduli using Molecular Dynamics simulations, and compare those to the Monte-Carlo method. The final…
Existence and growth of amorphous order in supercooled liquids approaching glass transition is a subject of intense research. Even after decades of work, there is still no clear consensus on the molecular mechanisms that lead to a rapid slowing down of liquid dynamics approaching this putative transition. The existence of a correlation length associated with amorphous order has recently been postulated and also been estimated using multi-point correlation functions which cannot be calculated easily in experiments. Thus the study of growing amorphous order remains mostly restricted to systems l…
We discuss the relaxation dynamics of a simple lattice gas model for glass-forming systems and show that with increasing density of particles this dynamics slows down very quickly. By monitoring the trajectory of tagged particles we find that their motion is very heterogeneous in space and time, leading to regions in space in which there is a fast dynamics and others in which it is slow. We determine how the geometric properties of these quickly relaxing regions depend on density and time. Motivated by this heterogeneous hopping dynamics, we use a simple model, a variant of a continuous time r…
We present a quantitative study of strain correlations in quiescent supercooled liquids and glasses. Recent two-dimensional computer simulations and experiments indicate that even supercooled liquids exhibit long-lived, long-range strain correlations. Here we investigate this issue in three dimensions via experiments on hard sphere colloids and molecular dynamics simulations of a glass forming binary Lennard Jones mixture. Both in the glassy state and in the supercooled regime, strain correlations are found to decay with a $1/r^{3}$ power-law behavior, reminiscent of elastic fields around an i…
