The use of the isoconfigurational ensemble to explore structure-dynamic correlations in supercooled liquids is examined. The statistical error of the dynamic propensity and its spatial distribution are determined. The authors present the spatial distribution of the particle non-Gaussian parameter as a measure of the intermittency with which particles exhibit their propensity for motion. The ensemble average of the direction of particle motion is introduced to establish the anisotropy of the dynamic propensity.
The configurational entropy is among the key observables to characterize experimentally the formation of a glass. Physically, it quantifies the multiplicity of metastable states in which an amorphous material can be found at a given temperature, and its temperature dependence provides a major thermodynamic signature of the glass transition, which is experimentally accessible. Measurements of the configurational entropy require, however, some approximations which have often led to ambiguities and contradictory results. Here we implement a novel numerical scheme to measure the configurational en…
When a liquid is cooled below its melting temperature, if crystallization is avoided, it forms a glass. This phenomenon, called glass transition, is characterized by a marked increase of viscosity, about 14 orders of magnitude, in a narrow temperature interval. The microscopic mechanism behind the glass transition is still poorly understood. However, recently, great advances have been made in the identification of cooperative rearranging regions, or dynamical heterogeneities, i.e. domains of the liquid whose relaxation is highly correlated. The growth of the size of these domains is now believ…
We propose a computational method to measure the configurational entropy in generic polydisperse glass-formers. In particular, our method resolves issues related to the diverging mixing entropy term due to a continuous polydispersity. The configurational entropy is measured as the difference between the well-defined fluid entropy and a more problematic glass entropy. We show that the glass entropy can be computed by a simple generalisation of the Frenkel-Ladd thermodynamic integration method, which includes permutations of the particle diameters. This approach automatically provides a physical…
Liquids relax extremely slowly upon approaching the glass state. One explanation is that an entropy crisis, due to the rarefaction of available states, makes it increasingly arduous to reach equilibrium in that regime. Validating this scenario is challenging, because experiments offer limited resolution, while numerical studies lag more than eight orders of magnitude behind experimentally-relevant timescales. In this work we not only close the colossal gap between experiments and simulations but manage to create in-silico configurations that have no experimental analog yet. Deploying a range o…
We perform stringent tests of thermodynamic theories of the glass transition over the experimentally relevant temperature regime for several simulated glass-formers. The swap Monte Carlo algorithm is used to estimate the configurational entropy and static point-to-set lengthscale, and careful extrapolations are used for the relaxation times. We first quantify the relation between configurational entropy and the point-to-set lengthscale in two and three dimensions. We then show that the Adam-Gibbs relation is generally violated in simulated models for the experimentally relevant time window. Co…
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 viscous slowing down of supercooled liquids that leads to glass formation can be considered as a classical, and is assuredly a thoroughly studied, example of a "jamming process". In this review, we stress the distinctive features characterizing the phenomenon. We also discuss the main theoretical approaches, with an emphasis on the concepts (free volume, dynamic freezing and mode-coupling approximations, configurational entropy and energy landscape, frustration) that could be useful in other areas of physics where jamming processes are encountered.
Diffusivity, a measure for how rapidly a fluid self-mixes, shows an intimate, but seemingly fragmented, connection to thermodynamics. On one hand, the "configurational" contribution to entropy (related to the number of mechanically-stable configurations that fluid molecules can adopt) has long been considered key for predicting supercooled liquid dynamics near the glass transition. On the other hand, the excess entropy (relative to ideal gas) provides a robust scaling for the diffusivity of fluids above the freezing point. Here we provide, to our knowledge, the first evidence that excess entro…
We make a first principle calculation of the fragility index $m$ of a simple liquid using the structure of the supercooled liquid as an input. Using the density functional theory (DFT) of classical liquids, the configurational entropy ${\cal S}_c$ is obtained for low degree of supercooling. We extrapolate this data to estimate the Kauzmann temperature $T_\mathrm{K}$ for the liquid. Using the Adam-Gibbs relation, we link the configurational entropy ${\cal S}_c$ to the relaxation time. The relaxation times are obtained from direct solutions of the equations of fluctuating nonlinear hydrodynamics…
Generation of equilibrium configurations is the major obstacle for numerical investigation of the slow dynamics in supercooled liquid states. The parallel tempering (PT) technique, originally proposed for the numerical equilibration of discrete spin-glass model configurations, has recently been applied in the study of supercooled structural glasses. We present an investigation of the ability of parallel tempering to properly sample the liquid configuration space at different temperatures, by mapping the PT dynamics into the dynamics of the closest local potential energy minima (inherent struct…
We formulate a microscopic, no adjustable parameter, theory of activated relaxation in supercooled liquids directly in terms of the repulsive and attractive forces within the framework of pair correlations. Under isochoric conditions, attractive forces can nonperturbatively modify slow dynamics, but at high enough density their influence vanishes. Under isobaric conditions, attractive forces play a minor role. High temperature apparent Arrhenius behavior and density-temperature scaling are predicted. Our results are consistent with recent isochoric simulations and isobaric experiments on a dee…
The supercooled liquid silicon, modeled by Stillinger-Weber potential, shows anomalous increase in heat capacity $C_p$, with a maximum $C_p$ value close to 1060 K at zero pressure. We study equilibration and relaxation of the supercooled SW Si, in the temperature range of 1060 K--1070 K at zero pressure. We find that as the relaxation of the metastable supercooled liquid phase initiates, a straight line region (SLR) is formed in cumulative potential energy distributions. The configurational temperature corresponding to the SLR is close to 1060 K, which was earlier identified as the freezing te…
Ozawa et. al [1] presented numerical results for the configurational entropy density, $s_c$, of a model glass-forming liquid in the presence of random pinning. The location of a "phase boundary" in the pin density ($c$) - temperature ($T$) plane, that separates an "ideal glass" phase from the supercooled liquid phase, is obtained by finding the points at which $s_c(T,c) \to 0$. According to the theoretical arguments by Cammarota et. al. [2], an ideal glass transition at which the $α$-relaxation time $τ_α$ diverges takes place when $s_c$ goes to zero. We have studied the dynamics of the same sy…
Tackling the low-temperature fate of supercooled liquids is challenging due to the immense timescales involved, which prevent equilibration and lead to the operational glass transition. Relating glassy behaviour to an underlying, thermodynamic phase transition is a long-standing open question in condensed matter physics. Like experiments, computer simulations are limited by the small time window over which a liquid can be equilibrated. Here we address the challenge of low temperature equilibration using trajectory sampling in a system undergoing a nonequilibrium phase transition. This transiti…
A steady shear flow can drive supercooled liquids into a non-equilibrium state. Using molecular dynamics simulations under steady shear flow superimposed with oscillatory shear strain for a probe, non-equilibrium mechanical responses are studied for a model supercooled liquid composed of binary soft spheres. We found that even in the strongly sheared situation, the supercooled liquid exhibits surprisingly isotropic responses to oscillating shear strains applied in three different components of the strain tensor. Based on this isotropic feature, we successfully constructed a simple two-mode Max…
Because of the isotropic and disordered nature of liquids, the anisotropy hidden in intermolecular interactions are often neglected. Accordingly, the order parameter describing a simple liquid has so far been believed to be only density. In contrast to this common sense, we propose that two order parameters, namely, density and bond order parameters, are required to describe the phase behavior of liquids since they intrinsically tend to form local bonds. This model gives us clear physical explanations for two poorly-understood phenomena in supercooled liquids: (i) large-scale density fluctuati…
We consider the problem of slow activation dynamics in glassy systems undergoing a random first order phase transition. Using an effective potential approach to supercooled liquids, we determine the spectrum of activation barriers for entropic droplets. We demonstrate that fluctuations of the configurational entropy and of the liquid glass surface tension are crucial to achieve an understanding of the barrier fluctuations in glassy systems and thus are ultimatively responsible for the broad spectrum of excitations and heterogeneous dynamics in glasses. In particular we derive a relation betwee…
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 study a one dimensional Coulomb system, where two charged colloids are neutralized by a collection of point counterions, with global neutrality. Temperature being given, two situations are addressed: the colloids are either kept at fixed positions (canonical ensemble), or the force acting on the colloids is fixed (isobaric-isothermal ensemble). The corresponding partition functions are worked out exactly, in view of determining which arrangement of counterions is optimal: how many counterions should be in the confined segment between the colloids? For the remaining ions outside, is there a …
We analyze the behavior of supercooled fluids under shear both theoretically and numerically. Theoretically, we generalize the mode-coupling theory of supercooled fluids to systems under stationary shear flow. Our starting point is the set of generalized fluctuating hydrodynamic equations with a convection term. A nonlinear integro-differential equation for the intermediate scattering function is constructed. This theory is applied to a two-dimensional colloidal suspension. The shear rate dependence of the intermediate scattering function and the shear viscosity is analyzed. We have also perfo…
A computational approach via implementation of the Principle Component Analysis (PCA) and Gaussian Mixture (GM) clustering methods from Machine Learning (ML) algorithms to identify domain structures of supercooled liquids is developed. Raw features data are collected from the coordination numbers of particles smoothed using its radial distribution function and are used as an order-parameter of disordered structures for GM clustering after dimensionality reduction from the PCA. To transfer the knowledge from features(structural) space to configurational space, another GM clustering is performed…
Liquid-liquid and liquid-vapor coexistence regions of various water models were determined by MC simulations of isotherms of density fluctuation restricted systems and by Gibbs ensemble MC simulations. All studied water models show multiple liquid-liquid phase transitions in the supercooled region: we observe two transitions of the TIP4P, TIP5P and SPCE model and three transitions of the ST2 model. The location of these phase transitions with respect to the liquid-vapor coexistence curve and the glass temperature is highly sensitive to the water model and its implementation. We suggest, that t…
First principles molecular dynamics simulations reveal a liquid-liquid phase transition in supercooled elemental silicon. Two phases coexist below $T_c\approx 1232K$. The low density phase is nearly tetra-coordinated, with a pseudogap at the Fermi surface, while the high density phase is more highly coordinated and metallic in nature. The transition is observed through the formation of van der Waals loops in pressure-volume isotherms below $T_c$.
We derive exact results for the rate of change of thermodynamic quantities, in particular the configurational specific heat at constant volume, $C_V$, along configurational adiabats (curves of constant excess entropy $S_{\textrm{ex}}$). Such curves are designated isomorphs for so-called Roskilde liquids, in view of the invariance of various structural and dynamical quantities along them. Their slope in a double logarithmic representation of the density-temperature phase diagram, $γ$ can be interpreted as one third of an effective inverse power-law potential exponent. We show that in liquids wh…
A novel liquid-liquid phase transition has been proposed and investigated in a wide variety of pure substances recently, including water, silica and silicon. From computer simulations using the Stillinger-Weber classical empirical potential, Sastry and Angell [1] demonstrated a first order liquid-liquid transition in supercooled silicon, subsequently supported by experimental and simulation studies. Here, we report evidence for a liquid-liquid critical end point at negative pressures, from computer simulations using the SW potential. Compressibilities exhibit a growing maximum upon lowering te…
We investigate the replica theory of the liquid-glass transition for a binary mixture of large and small additive hard spheres. We consider two different ansätze for this problem: the frozen glass ansatz (FGA) in whichs the exchange of large and small particles in a glass state is prohibited, and the exchange glass ansatz (EGA), in which it is allowed. We calculate the dynamical and thermodynamical glass transition points with the two ansätze. We show that the dynamical transition density of the FGA is lower than that of the EGA, while the thermodynamical transition density of the FGA is highe…
One of the most promising frameworks for understanding the anomalies of cold and supercooled water postulates the existence of two competing, interconvertible local structures. If the non-ideality in the Gibbs energy of mixing overcomes the ideal entropy of mixing of these two structures, a liquid-liquid phase transition, terminated at a liquid-liquid critical point, is predicted. Various versions of the "two-structure equation of state" (TSEOS) based on this concept have shown remarkable agreement with both experimental data for metastable, deeply supercooled water and simulations of molecula…
In this work, the short-time dynamics of simple liquid is explored both analytically and numerically with the focus on the interplay between the density fluctuations in a volume surrounding a chosen particle and its random walk motion. The particles interact via the Lennard-Jones potential with parameters corresponding to liquid argon. For large times, analytical calculations based on the fluctuation theory provides an explicit expression reproducing isothermal change of the self-diffusion coefficient in liquid argon corresponding to the experimental data. These results lead to the conclusion …
We investigate the relaxation mechanism of a supercooled tetrahedral liquid at its limit of stability using isothermal isobaric ($NPT$) Monte Carlo (MC) simulations. In similarity with systems which are far from equilibrium but near the onset of jamming [O'Hern et.al., Phys. Rev. Lett. {\bf 93}, 165702 (2004)], we find that the relaxation is characterized by two time-scales: the decay of long-wavelength (slow) fluctuations of potential energy is controlled by the the slope $[\partial (G/N)/\partial ϕ]$ of the Gibbs free energy ($G$) at a unique value of per particle potential energy $ϕ= ϕ_{mid…
We go over our finding that the dynamics at the noise-perturbed edge of chaos in logistic maps is comparable to that observed in supercooled liquids close to vitrification. That is, the three major features of glassy dynamics in structural glass formers, two-step relaxation, aging, and a relationship between relaxation time and configurational entropy, are displayed by orbits with vanishing Lyapunov exponent. The known properties in control-parameter space of the noise-induced bifurcation gap play a central role in determining the characteristics of dynamical relaxation at the chaos threshold.…
We observe, at low temperature, the appearance of propagating events that originate from the inter-conversion between adjacent four and five coordinated water molecules in supercooled liquid water, resulting in the migration of the coordination number five in a string-like fashion, creating rotational jumps along the way. The length of the connected events increases with lowering temperature. Each propagation event is terminated by a 3-coordinated species, present in a small number at large supercooling, which interacts cooperatively with 5-coordinated molecules to annihilate both the species.…
Experiments in bulk water confirm the existence of two local arrangements of water molecules with different densities, but, because of inevitable freezing at low temperature $T$, can not ascertain whether the two arrangements separate in two phases. To avoid the freezing, new experiments measure the dynamics of water at low $T$ on the surface of proteins, finding a crossover from a non-Arrhenius regime at high $T$ to a regime that is approximately Arrhenius at low $T$. Motivated by these experiments, Kumar et al. [Phys. Rev. Lett. 100, 105701 (2008)] investigated, by Monte Carlo simulations an…
We simulate the homogeneous nucleation of ice from supercooled liquid water at 220 K in the isobaric-isothermal ensemble using the MW monatomic water potential. Monte Carlo simulations using umbrella sampling are performed in order to determine the nucleation free energy barrier. We find the Gibbs energy profile to be relatively consistent with that predicted by classical nucleation theory; the free energy barrier to nucleation was determined to be ~18 kT and the critical nucleus comprised ~85 ice particles. Growth from the supercooled liquid gives clusters that are predominantly cubic, whilst…
We find that a system of particles interacting through a simple isotropic potential with a softened core is able to exhibit a rich phase behavior including: a liquid-liquid phase transition in the supercooled phase, as has been suggested for water; a gas-liquid-liquid triple point; a freezing line with anomalous reentrant behavior. The essential ingredient leading to these features resides in that the potential investigated gives origin to two effective core radii.
We present a new method of conducting molecular dynamics simulation in isothermal-isobaric ensemble based on Langevin equations of motion. The stochastic coupling to all particle and cell degrees of freedoms is introduced in a correct way, in the sense that the stationary configurational distribution is proved to be in consistent with that of the isothermal-isobaric ensemble. In order to apply the proposed method in computer simulations, a second order symmetric numerical integration scheme is developed by Trotter's splitting of the single-step propagator. Moreover, a practical guide of choosi…
A holonomic constraint is used to enforce a constant instantaneous configurational temperature on an equilibrium system. Three sets of equations of motion are obtained, differing according to the way in which the holonomic constraint is introduced and the phase space distribution function that is preserved by the dynamics. Firstly, Gauss' principle of least constraint is used, and it is shown that it does not preserve the canonical distribution. Secondly, a modified Hamiltonian is used to find a dynamics that provides a restricted microcanonical distribution. Lastly, we provide equations that …
