Recent numerical studies on glassy systems provide evidences for a population of non-Goldstone modes (NGMs) in the low-frequency spectrum of the vibrational density of states $D(ω)$. Similarly to Goldstone modes (GMs), i. e., phonons in solids, NGMs are soft low-energy excitations. However, differently from GMs, NGMs are localized excitations. Here we first show that the parental temperature $T^*$ modifies the GM/NGM ratio in $D(ω)$. In particular, the phonon attenuation is reflected in a parental temperature dependency of the exponent $s(T^*)$ in the low-frequency power law $D(ω) \sim ω^{s(T^*)}$, with $2 \leq s(T^*) \leq 4 $. Secondly, by comparing $s(T^*)$ with $s(p)$, i. e., the same quantity obtained by pinning \mttp{a} $p$ particle fraction, we suggest that $s(T^*)$ reflects the presence of dynamical heterogeneous regions of size $ξ^3 \propto p$. Finally, we provide an estimate of $ξ$ as a function of $T^*$, finding a mild power law divergence, $ξ\sim (T^* - T_d)^{-α/3}$, with $T_d$ the dynamical crossover temperature and $α$ falling in the range $α\in [0.8,1.0]$.
Stochastic-Beta-Relaxation (SBR) provides a characterisation of the glass crossover in discontinuous Spin-Glasses and Supercoooled liquid. Notably it can be derived through a rigorous computation from a dynamical Landau theory. In this paper I will discuss the precise meaning of this connection in a language that does not require familiarity with statistical field theory. I will discuss finite-size corrections in mean-field Spin-Glass models and loop corrections in finite-dimensional models that are both described by the dynamical Landau theory considered. Then I will argue that the same Landa…
In these lectures, which were presented at "Soft and Fragile Matter, Nonequilibrium Dynamics, Metastability and Flow" University of St. Andrews, 8 July - 22 July, 1999, I give an introduction to the physics of supercooled liquids and glasses and discuss some computer simulations done to investigate these systems.
Molecular dynamics simulations have been performed on TIP4P/2005 supercooled water to investigate the molecular diffusion and shear viscosity at various timescales and assess the Stokes-Einstein (SE) and Stokes-Einstein-Debye (SED) relations. For this purpose, we calculated various time correlation functions, such as the mean-squared displacement, stress relaxation function, density correlation function, hydrogen-bond correlation function, rotational correlation function of molecular orientation, non-Gaussian parameter, and four-point correlation function. Our study of the SE and SED relations…
The dynamics of supercooled liquid and glassy systems are usually studied within the Lagrangian representation, in which the positions and velocities of distinguishable interacting particles are followed. Within this representation, however, it is difficult to define measures of spatial heterogeneities in the dynamics, as particles move in and out of any one given region within long enough times. It is also non-transparent how to make connections between the structural glass and the spin glass problems within the Lagrangian formulation. We propose an Eulerian formulation of supercooled liquids…
A formally exact set of equations is derived for the description of nonequilibrium phenomena in classical liquids and glasses. With the help of a non equilibrium projection operator formalism, the correlation functions and fluctuation propagators are expressed in terms of memory functions and time dependent collective frequencies. This formally exact set of equations is approximated by applying mode coupling approximations to the memory functions. The resulting set of equations for wavevector dependent correlation functions, fluctuation propagators and one-time structure factors $S_q(t)$ gener…
For a model glass-former we demonstrate via computer simulations how macroscopic dynamic quantities can be inferred from a PEL analysis. The essential step is to consider whole superstructures of many PEL minima, called metabasins, rather than single minima. We show that two types of metabasins exist: some allowing for quasi-free motion on the PEL (liquid-like), the others acting as traps (solid-like). The activated, multi-step escapes from the latter metabasins are found to dictate the slowing down of dynamics upon cooling over a much broader temperature range than is currently assumed.
We review the inherent structure thermodynamical formalism and the formulation of an equation of state for liquids in equilibrium based on the (volume) derivatives of the statistical properties of the potential energy surface. We also show that, under the hypothesis that during aging the system explores states associated to equilibrium configurations, it is possible to generalize the proposed equation of state to out-of-equilibrium conditions. The proposed formulation is based on the introduction of one additional parameter which, in the chosen thermodynamic formalism, can be chosen as the loc…
After a brief introduction to the dynamics of supercooled liquids, we discuss some of the advantages and drawbacks of computer simulations of such systems. Subsequently we present the results of computer simulations in which the dynamics of a fragile glass former, a binary Lennard-Jones system, is compared to the one of a strong glass former, SiO_2. This comparison gives evidence that the reason for the different temperature dependence of these two types of glass formers lies in the transport mechanism for the particles in the vicinity of T_c, the critical temperature of mode-coupling theory. …
Recent work suggests that Heisenberg spin glasses may belong to the same universality class than structural glasses. Indeed, finding a lattice equivalent for supercooled liquids would probably allow easier numerical and analytical studies, that may help to answer long-standing questions on the glass transition. Supercooled liquids have many peculiar behaviors that should be found in the paramagnetic phase of Heisenberg spin glasses if the analogy between the two systems holds. It is with this motivation that we undertake a study of the paramagnetic phase of Heisenberg spin glasses. We shall em…
We investigate the properties of the low-frequency spectrum in the density of states $D(ω)$ of a three-dimensional model glass former. To magnify the Non-Debye sector of the spectrum, we introduce a random pinning field that freezes a finite particle fraction in order to break the translational invariance and shifts all the vibrational frequencies of the extended modes towards higher frequencies. We show that Non-Debye soft localized modes progressively emerge as the fraction $p$ of pinned particles increases. Moreover, the low-frequency tail of $D(ω)$ goes to zero as a power law $ω^{δ(p)}$, w…
Anomalous Values of Debye temperature have been obtained from Lamb Mossbauer factor measurements of Ge-Se-Ag glasses. We show that this anomaly may arise due to the presence of anharmonic potential at the high spin ferrous site. In this paper, we use q Lamb Mossbauer factor and anharmonic Lamb Mossbauer factor to study this anharmoncity.
Using molecular dynamics simulation, we have calculated the pressure dependence of the diffusion constant in a binary Lennard-Jones Glass. We observe four temperature regimes. The apparent activation volume drops from high values in the hot liquid to a plateau value. Near the critical temperature of the mode coupling theory it rises steeply, but in the glassy state we find again small values, similar to the ones in the liquid. The peak of the activation volume at the critical temperature is in agreement with the prediction of mode coupling theory.
A kinetic Monte Carlo (KMC) method is used to study the structural properties and dynamics of a supercooled binary Lennard-Jones liquid around the glass transition temperature. This technique permits us to explore the potential energy surface and barrier distributions without suffering the exponential slowing down at low temperature that affects molecular dynamics simulations. In agreement with previous studies we observe a distinct change in behaviour around $T=0.45$, close to the dynamical transition temperature $T_c$ of mode coupling theory (MCT). Below this temperature the number of differ…
Usually, supercooled liquids and glasses are thermodynamically unstable against crystallization. Classical nucleation theory (CNT) has been used to describe the crystallization dynamics of supercooled liquids. However, recent studies on overcompressed hard spheres show that their crystallization dynamics are intermittent and mediated by avalanche-like rearrangements of particles, which largely differ from the CNT. These observations suggest that the crystallization times of deeply supercooled liquids or glasses cannot be described by the CNT, but this point has not yet been studied in detail. …
We present a first principle scheme to compute the rigidity, i. e. the shear-modulus of structural glasses at finite temperatures using the cloned liquid theory, which combines the replica theory and the liquid theory. With the aid of the replica method which enables disentanglement of thermal fluctuations in liquids into intra-state and inter-state fluctuations, we extract the rigidity of metastable amorphous solid states in the supercooled liquid and glass phases. The result can be understood intuitively without replicas. As a test case, we apply the scheme to the supercooled and glassy stat…
We review the Random First Order Transition Theory of the glass transition, emphasizing the experimental tests of the theory. Many distinct phenomena are quantitatively predicted or explained by the theory, both above and below the glass transition temperature $T_g$. These include: the viscosity catastrophe and heat capacity jump at $T_g$, and their connection; the non-exponentiality of relaxations and their correlation with the fragility; dynamic heterogeneity in supercooled liquids owing to the mosaic structure; deviations from the Vogel-Fulcher law, connected with strings or fractral cooper…
Below 1 K, the specific heat Cp of glasses depends approximately linearly on temperature T, in contrast with the cubic dependence observed in crystals, and which is well understood in terms of the Debye theory. That linear contribution has been ascribed to the existence of two-level systems as postulated by the Tunnelling Model. Therefore, a least-squares linear fit Cp = C_1 T + C_3 T^3 has been traditionally used to determine the specific-heat coefficients, though systematically providing calorimetric cubic coefficients exceeding the elastic coefficients obtained from sound-velocity measureme…
We combine Creutz energy conservation with Kawasaki spin exchange to simulate the microcanonical dynamics of a system of interacting particles. Relaxation occurs via Glauber spin-flip activation using a self-consistent temperature. Heterogeneity in the dynamics comes from finite-size constraints on the spin exchange that yield a distribution of correlated regions. The simulation produces a high-frequency response that can be identified with the boson peak, and a lower-frequency peak that contains non-Debye relaxation and non-Arrhenius activation, similar to the primary response of supercooled …
Besides the dynamical slowing down signaled by an enormous increase of the viscosity approaching the glass transition, structural glasses show interesting anomalous thermodynamic features at low temperatures that hint at peculiar deviations from Debye's law at low enough frequencies. Theory, numerical simulations, and experiments suggest that deviation from Debye's law is due to soft-localized glassy modes that populate the low-frequency spectrum. We study the localization properties of the low-frequency modes in a three-dimensional supercooled liquid model. The density of states $D(ω)$ is com…
The random first order transition theory of the dynamics of supercooled liquids is extended to treat aging phenomena in nonequilibrium structural glasses. A reformulation of the idea of ``entropic droplets'' in terms of libraries of local energy landscapes is introduced which treats in a uniform way the supercooled liquid (reproducing earlier results) and glassy regimes. The resulting microscopic theory of aging makes contact with the Nayaranaswamy-Moynihan-Tool nonlinear relaxation formalism and the Hodge-Scherer extrapolation of the Adam-Gibbs formula, but deviations from both approaches are…
The low-temperature thermal properties of dielectric crystals are governed by acoustic excitations with large wavelengths that are well described by plane waves. This is the Debye model, which rests on the assumption that the medium is an elastic continuum, holds true for acoustic wavelengths large on the microscopic scale fixed by the interatomic spacing, and gradually breaks down on approaching it. Glasses are characterized as well by universal low-temperature thermal properties, that are however anomalous with respect to those of the corresponding crystalline phases. Related universal anoma…
Calorimetric experiments on network glasses provide information on the ergodicity (landscape) temperature of supercooled liquids and can be compared with a recent theory developed by Hall and Wolynes [PRL90, 085505 (2003)]
We present a phase diagram for water confined to cylindrical silica nanopores in terms of pressure, temperature and pore radius. The confining cylindrical wall is hydrophilic and disordered, which has a destabilizing effect on ordered water structure. The phase diagram for this class of systems is derived from general arguments, with parameters taken from experimental observations and computer simulations and with assumptions tested by computer simulation. Phase space divides into three regions: a single liquid, a crystal-like solid, and glass. For large pores, radii exceeding 1 nm, water exhi…
In amorphous materials, groups of particles can rearrange locally into a new stable configuration. Such elementary excitations are key as they determine the response to external stresses, as well as to thermal and quantum fluctuations. Yet, understanding what controls their geometry remains a challenge. Here we build a scaling description of the geometry and energy of low-energy excitations in terms of the distance to an instability, as predicted for instance at the dynamical transition in mean field approaches of supercooled liquids. We successfully test our predictions in ultrastable compute…
Liquid is represented as complicated system of disclinations according to defect description of liquids and glasses. The expressions for the linear disclination field of an arbitrary form and energy of inter-disclination interaction are derived in the framework of gauge theory of defects. It allows us to describe liquid as a disordered system of topological moments and reduce this model to the Edwards--Anderson model with large-range interaction. Within the framework of this approach vitrifying is represented as a "hierarchical" phase transition. The suggested model allows us to explain the pr…
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 …
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…
Exploring structural order in disordered systems including liquids and glasses is an intriguing but challenging issue in condensed matter physics. Here we construct a new parameter based on the angular distribution function of particles and show that this new orientational order has significantly higher correlation with dynamic heterogeneity compared to a translational parameter based on the radial distribution functions in colloidal glasses. The gradual development of orientational and translational order in supercooled liquids shows that the higher correlation between orientational order and…
We construct a quantum mechanical model of perfectly isotropic amorphous solids as fuzzy crystals and establish an analytical theory of vibrations for glasses at low temperature. Our theoretical framework relies on the basic principle that the disorder in a glass is similar to the disorder in a classical fluid, while the latter is mathematically encoded by noncommutative coordinates in the Lagrange formulation of fluid mechanics. We find that the density of states in the acoustic branches flattens significantly, leading naturally to a boson peak in the specific heat as a manifestation of a van…
We discuss a microscopic scheme to compute the rigidity of glasses or the plateau modulus of supercooled liquids by twisting replicated liquids. We first summarize the method in the case of harmonic glasses with analytic potentials. Then we discuss how it can be extended to the case of repulsive contact systems : the hard sphere glass and related systems with repulsive contact potentials which enable the jamming transition at zero temperature. For the repulsive contact systems we find entropic rigidity which behaves similarly as the pressure in the low temperature limit: it is proportional to …
We numerically study a nondisordered lattice spin system with a first order liquid-crystal transition, as a model for supercooled liquids and glasses. Below the melting temperature the system can be kept in the metastable liquid phase, and it displays a dynamic phenomenology analogous to fragile supercooled liquids, with stretched exponential relaxation, power law increase of the relaxation time and high fragility index. At an effective spinodal temperature Tsp the relaxation time exceeds the crystal nucleation time, and the supercooled liquid loses stability. Below Tsp liquid properties canno…
Critical slowing down dynamics of supercooled glass-forming liquids is usually understood at the mean-field level in the framework of Mode Coupling Theory, providing a two-time relaxation scenario and power-law behaviors of the time correlation function at dynamic criticality. In this work we derive critical slowing down exponents of spin-glass models undergoing discontinuous transitions by computing their Gibbs free energy and connecting the dynamic behavior to static "in-state" properties. Both the spherical and Ising versions are considered and, in the simpler spherical case, a generalizati…
We use the general statement of the second law applied to an isolated system, the glass in an extremely large medium, to prove that the entropy of the glass must decrease with time during its relaxation towards the supercooled liquid state. This result contradicts the claim of Mauro et al and their computational result of the entropy, according to which their entropy of the glass increases. Our approach using the isolated system completely bypasses the issue of ergodicity loss in glasses, as discussed in the comment.
According to the Random First Order Transition (RFOT) theory of glasses, the barriers for activated dynamics in supercooled liquids vanish as the temperature of a viscous liquid approaches the dynamical transition temperature from below. This occurs due to a decrease of the surface tension between local meta-stable molecular arrangements much like at a spinodal. The dynamical transition thus represents a crossover from the low $T$ activated bevavior to a collisional transport regime at high $T$. This barrier softening explains the deviation of the relaxation times, as a function of temperature…
A relaxation process, with the associated phenomenology of sound attenuation and sound velocity dispersion, is found in a simulated harmonic Lennard-Jones glass. We propose to identify this process with the so called microscopic (or instantaneous) relaxation process observed in real glasses and supercooled liquids. A model based on the memory function approach accounts for the observation, and allows to relate to each others: 1) the characteristic time and strength of this process, 2) the low frequency limit of the dynamic structure factor of the glass, and 3) the high frequency sound attenuat…
The impact of severe plastic deformation by high-pressure torsion on the relaxation of the glassy and supercooled liquid states of Pd$_{40}$Ni$_{40}$P$_{20}$ was investigated using a combination of differential scanning calorimetry, low-temperature heat capacity and fluctuation electron microscopy. The changes in the calorimetric signals due to deformation and subsequent heat treatments were analyzed and a correlation between deformation (rejuvenation) and annealing (relaxation) was found in relation to medium-range order (MRO). Moreover, a coupling between the occurrence of an exothermic peak…
The low-temperature properties of glasses present important differences with respect to crystalline matter. In particular, models such as the Debye model of solids, which assume the existence of an underlying regular lattice, predict that the specific heat of solids varies with the cube of temperature at low temperatures. Since the 1970s' at least, it is a well established experimental fact that the specific heat of glasses is instead just linear in $T$ at $T \sim 1K$, and presents a pronounced peak when normalized by $T^{3}$, known as the boson peak. Here we present a new approach which sugge…
We propose an atomistic model for correlated particle dynamics in liquids and glasses predicting both slow stretched-exponential relaxation (SER) and fast compressed-exponential relaxation (CER). The model is based on the key concept of elastically interacting local relaxation events. SER is related to slowing down of dynamics of local relaxation events as a result of this interaction, whereas CER is related to the avalanche-like dynamics in the low-temperature glass state. The model predicts temperature dependence of SER and CER seen experimentally and recovers the simple, Debye, exponential …
We show that a {\em vibrational instability} of the spectrum of weakly interacting quasi-local harmonic modes creates the maximum in the inelastic scattering intensity in glasses, the Boson peak. The instability, limited by anharmonicity, causes a complete reconstruction of the vibrational density of states (DOS) below some frequency $ω_c$, proportional to the strength of interaction. The DOS of the new {\em harmonic modes} is independent of the actual value of the anharmonicity. It is a universal function of frequency depending on a single parameter -- the Boson peak frequency, $ω_b$ which is…
Below the melting temperature $T_m$ crystals are the stable phase of typical elemental or molecular systems. However, cooling down a liquid below $T_m$, crystallization is anything but inevitable. The liquid can be supercooled, eventually forming a glass below the glass transition temperature $T_g$. Despite their long lifetimes and the presence of strong barriers that produces an apparent stability, supercooled liquids and glasses remain intrinsically metastable state and thermodynamically unstable towards the crystal. Here we investigated the isothermal crystallization kinetics of the prototy…
The origins of rapid dynamical slow down in glass forming liquids in the growth of static length scales, possibly associated with identifiable structural ordering, is a much debated issue. Growth of medium range crystalline order (MRCO) has been observed in various model systems to be associated with glassy behaviour. Such observations raise the question about the eventual state reached by a glass former, if allowed to relax for sufficiently long times. Is a slowly growing crystalline order responsible for slow dynamics? Are the molecular mechanisms for glass transition in liquids with and wit…
Glasses possess more low-frequency vibrational modes than predicted by Debye theory. These excess modes are crucial for the understanding the low temperature thermal and mechanical properties of glasses, which differ from those of crystalline solids. Recent simulational studies suggest that the density of the excess modes scales with their frequency $ω$ as $ω^4$ in two and higher dimensions. Here, we present extensive numerical studies of two-dimensional model glass formers over a large range of glass stabilities. We find that the density of the excess modes follows $D_\text{exc}(ω)\sim ω^2 $ …
We present a novel mechanism for the anomalous behaviour of the specific heat in low-temperature amorphous solids. The analytic solution of a mean-field model belonging to the same universality class as high-dimensional glasses, the spherical perceptron, suggests that there exists a crossover temperature above which the specific heat scales linearly with temperature while below it a cubic scaling is displayed. This relies on two crucial features of the phase diagram: (i) The marginal stability of the free-energy landscape, which induces a gapless phase responsible for the emergence of a power-…
Aging phenomena have been studied in very different materials like polymers, supercooled liquids or disordered orientational crystals. We recall here the main features of aging in spin glasses, and use this example of magnetic systems as a guideline for the description of the others. A particular attention is put on the sensitivity of aging to the cooling rate and to temperature variations. This allows us to point out differences between temperature specific processes, yielding ``rejuvenation and memory effects'' as known in spin glasses, and domain growth processes, giving cumulative contribu…
Analytical representations in the time and frequency domains are derived for the most frequently used phenomenological fit functions for non-Debye relaxation processes. In the time domain the relaxation functions corresponding to the complex frequency dependent Cole-Cole, Cole-Davidson and Havriliak-Negami susceptibilities are also represented in terms of $H$-functions. In the frequency domain the complex frequency dependent susceptibility function corresponding to the time dependent stretched exponential relaxation function is given in terms of $H$-functions. The new representations are usefu…
We numerically study the evolution of the vibrational density of states $D(ω)$ of zero-temperature glasses when their kinetic stability is varied over an extremely broad range, ranging from poorly annealed glasses obtained by instantaneous quenches from above the onset temperature, to ultrastable glasses obtained by quenching systems thermalised below the experimental glass temperature. The low-frequency part of the density of states splits between extended and quasi-localized modes. Extended modes exhibit a boson peak crossing over to Debye behaviour ($D(ω) \sim ω^2$) at low-frequency, with a…
Supercooled liquids give rise, by homogeneous nucleation, to solid superclusters acting as building blocks of glass, ultrastable glass, and glacial glass phases before being crystallized. Liquid-to-liquid phase transitions begin to be observed above the melting temperature Tm as well as critical undercooling depending on critical overheating (Tm-T)/Tm. Solid nuclei exist above Tm and melt by homogeneous nucleation of liquid instead of surface melting. The Gibbs free energy change predicted by the classical nucleation equation is completed by an additional enthalpy which stabilize these solid e…
The steady state values of the viscosity and the intrinsic ionic-conductivity of quenched melts are computed, in terms of independently measurable quantities. The frequency dependence of the ac dielectric response is estimated. The discrepancy between the corresponding characteristic relaxation times is only apparent; it does not imply distinct mechanisms, but stems from the intrinsic barrier distribution for $α$-relaxation in supercooled fluids and glasses. This type of intrinsic ``decoupling'' is argued not to exceed four orders in magnitude, for known glassformers. We explain the origin of …
We have analyzed a non-randomly frustrated spin model which exhibits behavior remarkably similar to the phenomenology of structural glasses. The high-temperature disordered phase undergoes a strong first-order transition to a long-range ordered structure. Using Monte Carlo simulations, we have studied the behavior of the supercooled state by quenching to temperatures below this transition temperature. For a range of supercooling, the system remains ergodic and exhibits dynamics characteristic of supercooled liquids. Below a certain characteristic temperature, however, the system freezes into a…
The density of vibrational states $g(ω)$ of an amorphous system is studied by using the random-matrix theory. Taking into account the most important correlations between elements of the random matrix of the system, equations for the density of vibrational states $g(ω)$ are obtained. The analysis of these equations shows that in the low-frequency region the vibrational density of states has the Debye behavior $g(ω) \sim ω^2$. In the higher frequency region, there is the boson peak as an additional contribution to the density of states. The obtained equations are in a good agreement with the num…
