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Raffaele Pastore

Publications and source records attributed to Raffaele Pastore.

At least 19 recordsLinked to original sources

At low temperatures, glass-forming liquids relax in a simple way

Glass-forming liquids have only a modest tendency to crystallize and hence their dynamics can be studied even below the melting temperature. The relaxation dynamics of most of these liquids shows at a temperature $T_c$, somewhat above the glass-transition temperature $T_g$, a crossover, which indicates the conjunction of two different dynamical regimes. For temperatures slightly above $T_c$, experiments and computer simulations have extensively probed this dynamics on the particle level and identified several universal scaling laws that are often compatible with theoretical predictions. Using large scale computer simulations we extend these studies to temperatures below $T_c$ and find that the relaxation mechanism is qualitatively different from the one found at higher temperatures. We identify new scaling laws that allow to give a simple description of the relaxation dynamics at very low $T$s. Specifically we reveal that the cage-escape process is related to rare but large particle displacements that give rise to a distinctive sub-diffusive power-law in the time correlation functions. This insight helps to advance our understanding on the relaxation dynamics of glass-forming systems at temperatures that are close to the experimental glass transition.

cond-mat.soft

Microscopic structure and dynamics of shear-thinning suspensions of polydisperse, repulsive vesicles

We investigate the rheology, microscopic structure, and dynamics of an industrially relevant dispersion made of cationic surfactant vesicles, from dilute to concentrated conditions. We find that these suspensions exhibit a shear-thinning behavior at relatively low concentrations. At the microscale, this corresponds to a well-defined transition in both the structure, marked by the appearance of a peak in the static structure factor, and the dynamics, which slow down and develop a two-step decay in the correlation functions. This low-concentration transition is particularly surprising in light of experiments showing that for surfactant vesicles of similar composition the interactions should be purely repulsive. This leads us to propose that the observed structural and dynamic transition could arise, as an entropic effect, from the large sample polydispersity coupled to crowding. The shear-thinning behavior is thus interpreted as the nonlinear response of this transient structure to the imposed flow. Our work suggests that similar effects might be a generic feature of dense, highly polydisperse charged suspensions.

cond-mat.soft

Rheological signatures of a glass-glass transition in an aging colloidal clay

The occurrence of non-equilibrium transitions between arrested states has recently emerged as an intriguing issue in the field of soft glassy materials. The existence of one such transition has been suggested for aging colloidal clays (Laponite$^{\circledR}$ suspensions) at weight concentration 3.0%, although further experimental evidences are necessary to validate this scenario. Here, we test the occurrence of this transition for spontaneously aged (non-rejuvenated) samples, by exploiting the rheological tools of Dynamical Mechanical Analysis. On imposing consecutive compression cycles to differently aged clay suspensions, we find that a quite abrupt change of rheological parameters occurs for ages around three days. For the Young and elastic moduli, the change with the waiting time is essentially independent from the deformation rate, whereas other "fluid-like" properties, such as the loss modulus, do clearly display some rate dependence. We also show that the crossover identified by rheology coincides with deviations of the relaxation time (obtained through X-Ray Photon Correlation Spectroscopy) from its expected monotonic increase with aging. Thus, our results robustly support the existence of a glass-glass transition in aging colloidal clays, highlighting characteristic features of of their viscoelastic behaviour.

cond-mat.soft

Supercooled liquids are Fickian yet non-Gaussian

Reply to "Comment on 'Fickian non-Gaussian diffusion in glass-forming liquids' ". In [ArXiv:2210.07119v1], Berthier et al. questioned the findings of our letter [Phys. Rev. Lett. 128, 168001 (2022)], concerning the existence and the features of Fickian non-Gaussian diffusion in glass-forming liquids. Here we demonstrate that their arguments are either wrong, or not meaningful to our scope. Thus, we fully confirm the validity and novelty of our results.

cond-mat.stat-mech

Concentrated suspensions of Brownian beads in water: dynamic heterogeneities trough a simple experimental technique

Concentrated suspensions of Brownian hard-spheres in water are an epitome for understanding the glassy dynamics of both soft materials and supercooled molecular liquids. From an experimental point of view, such systems are especially suited to perform particle tracking easily, and, therefore, are a benchmark for novel optical techniques, applicable when primary particles cannot be resolved. Differential Variance Analysis (DVA) is one such novel technique that simplifies significantly the characterization of structural relaxation processes of soft glassy materials, since it is directly applicable to digital image sequences of the sample. DVA succeeds in monitoring not only the average dynamics, but also its spatio-temporal fluctuations, known as dynamic heterogeneities. In this work, we study the dynamics of dense suspensions of Brownian beads in water, imaged through digital video-microscopy, by using both DVA and single-particle tracking. We focus on two commonly used signatures of dynamic heterogeneities: the dynamic susceptibility, $χ_4$, and the non-Gaussian parameter, $α_2$. By direct comparison of these two quantities, we are able to highlight similarities and differences. We do confirm that $χ_4$ and $α_2$ provide qualitatively similar information, but we find quantitative discrepancies in the scalings of characteristic time and length scale on approaching the glass transition.

cond-mat.soft

Origin of Charge Separation at Organic Photovoltaic Heterojunctions: A Mesoscale Quantum Mechanical View

The high efficiency of charge generation within organic photovoltaic blends apparently contrasts with the strong "classical" attraction between newly formed electron-hole pairs. Several factors have been identified as possible facilitators of charge dissociation, such as quantum mechanical coherence and delocalization, structural and energetic disorder, built-in electric fields, nanoscale intermixing of the donor and acceptor components of the blends. Our mesoscale quantum-chemical model allows an unbiased assessment of their relative importance, through excited-state calculations on systems containing thousands of donor and acceptor sites. The results on several model heterojunctions confirm that the classical model severely overestimates the binding energy of the electron-hole pairs, produced by vertical excitation from the electronic ground state. Using physically sensible parameters for the individual materials, we find that the quantum mechanical energy difference between the lowest interfacial charge transfer states and the fully separated electron and hole is of the order of the thermal energy.

cond-mat.mes-hall

Cage Size and Jump Precursors in Glass-Forming Liquids: Experiment and Simulations

Glassy dynamics is intermittent, as particles suddenly jump out of the cage formed by their neighbours, and heterogeneous, as these jumps are not uniformly distributed across the system. Relating these features of the dynamics to the diverse local environments explored by the particles is essential to rationalize the relaxation process. Here we investigate this issue characterizing the local environment of a particle with the amplitude of its short time vibrational motion, as determined by segmenting in cages and jumps the particle trajectories. Both simulations of supercooled liquids and experiments on colloidal suspensions show that particles in large cages are likely to jump after a small time-lag, and that, on average, the cage enlarges shortly before the particle jumps. At large time-lags, the cage has essentially a constant value, which is smaller for longer-lasting cages. Finally, we clarify how this coupling between cage size and duration controls the average behaviour and opens the way to a better understanding of the relaxation process in glass--forming liquids.

cond-mat.soft

Relaxation functions and dynamical heterogeneities in a model of chemical gel interfering with glass transition

We investigate the heterogeneous dynamics in a model, where chemical gelation and glass transition interplay, focusing on the dynamical susceptibility. Two independent mechanisms give raise to the correlations, which are manifested in the dynamical susceptibility: one is related to the presence of permanent clusters, while the other is due to the increase of particle crowding as the glass transition is approached. The superposition of these two mechanisms originates a variety of different behaviours. We show that these two mechanisms can be unentangled considering the wave vector dependence of the dynamical susceptibility.

cond-mat.soft

Differential Variance Analysis of soft glassy materials: a direct method to quantify and visualize dynamic heterogeneities

Many amorphous materials show spatially heterogenous dynamics, as different regions of the same system relax at different rates. Such a signature, known as Dynamic Heterogeneity, has been crucial to understand the jamming transition in simple model systems and, currently, is considered very promising to characterize more complex fluids of industrial and biological relevance. Unfortunately, measurements of dynamic heterogeneities typically require sophysticated experimental set-ups and are performed by few specialized groups. It is now possible to quantitatively characterize the relaxation process and the emergence of dynamic heterogeneities using a straightforward method, here validated on video microscopy data of hard-sphere colloidal glasses. We call this method Differential Variance Analysis (DVA), since it focuses on the variance of the differential frames, obtained subtracting images at different lag-times. Moreover, direct visualization of dynamic heterogeneities naturally appears in the differential frames, when the lag-time is set to the one corresponding to the maximum dynamic susceptibility. This approach opens the way to effectively characterize and tailor a wide variety of soft materials, from complex formulated products to biological tissues.

cond-mat.soft

Cage-jump motion reveals universal dynamics and non-universal structural features in glass forming liquids

The sluggish and heterogeneous dynamics of glass forming liquids is frequently associated to the transient coexistence of two phases of particles, respectively with an high and low mobility. In the absence of a dynamical order parameter that acquires a transient bimodal shape, these phases are commonly identified empirically, which makes difficult investigating their relation with the structural properties of the system. Here we show that the distribution of single particle diffusivities can be accessed within a Continuous Time Random Walk description of the intermittent motion, and that this distribution acquires a transient bimodal shape in the deeply supercooled regime, thus allowing for a clear identification of the two coexisting phase. In a simple two-dimensional glass forming model, the dynamic phase coexistence is accompanied by a striking structural counterpart: the distribution of the crystalline-like order parameter becomes also bimodal on cooling, with increasing overlap between ordered and immobile particles. This simple structural signature is absent in other models, such as the three-dimesional Kob-Andersen Lennard-Jones mixture, where more sophisticated order parameters might be relevant. In this perspective, the identification of the two dynamical coexisting phases opens the way to deeper investigations of structure-dynamics correlations.

cond-mat.soft

Cluster structure and dynamics in gels and glasses

The dynamical arrest of gels is the consequence of a well defined structural phase transition, leading to the formation of a spanning cluster of bonded particles. The dynamical glass transition, instead, is not accompanied by any clear structural signature. Nevertheless, both transitions are characterized by the emergence of dynamical heterogeneities. Reviewing recent results from numerical simulations, we discuss the behavior of dynamical heterogeneities in different systems and show that a clear connection with the structure exists in the case of gels. The emerging picture may be also relevant for the more elusive case of glasses. We show, as an example, that the relaxation process of a simple glass-forming model can be related to a reverse percolation transition and discuss further perspective in this direction.

cond-mat.soft

Spatial correlations of elementary relaxation events in glass-forming liquids

The dynamical facilitation scenario, by which localized relaxation events promote nearby relaxation events in an avalanching process, has been suggested as the key mechanism connecting the microscopic and the macroscopic dynamics of structural glasses. Here we investigate the statistical features of this process via the numerical simulation of a model structural glass. First we show that the relaxation dynamics of the system occurs through particle jumps that are irreversible, and that cannot be decomposed in smaller irreversible events. Then we show that each jump does actually trigger an avalanche. The characteristic of this avalanche change on cooling, suggesting that the relaxation dynamics crossovers from a noise dominated regime where jumps do not trigger other relaxation events, to a regime dominated by the facilitation process, where a jump trigger more relaxation events.

cond-mat.soft

Particle jumps in structural glasses

Particles in structural glasses rattle around temporary equilibriumpositions, that seldom change through a process which is much faster than the relaxation time, known as particle jump. Since the relaxation of the system is due to the accumulation of many such jumps, it could be possible to connect the single particle short time motion to the macroscopic relaxation by understanding the features of the jump dynamics. Here we review recent results in this research direction, clarifying the features of particles jumps that have been understood and those that are still under investigation, and examining the role of particle jumps in different theories of the glass transition.

cond-mat.soft

Connecting short and long time dynamics in hard-sphere-like colloidal glasses

Glass-forming materials are characterized by an intermittent motion at the microscopic scale. Particles spend most of their time rattling within the cages formed by their neighbors, and seldom jump to a different cage. In molecular glass formers the temperature dependence of the jump features, such as the average caging time and jump length, characterizes the relaxation processes and allows for a short-time prediction of the diffusivity. Here we experimentally investigate the cage-jump motion of a two-dimensional hard-sphere-like colloidal suspension, where the volume fraction is the relevant parameter controlling the slowing down of the dynamics. We characterize the volume fraction dependence of the cage-jump features and show that, as in molecular systems, they allow for a short time prediction of the diffusivity.

cond-mat.soft

From cage-jump motion to macroscopic diffusion in supercooled liquids

The evaluation of the long term stability of a material requires the estimation of its long-time dynamics. For amorphous materials such as structural glasses, it has proven difficult to predict the long-time dynamics starting from static measurements. Here we consider how long one needs to monitor the dynamics of a structural glass to predict its long--time features. We present a detailed characterization of the statistical features of the single-particle intermittent motion of structural glasses, and show that single--particle jumps are the irreversible events leading to the relaxation of the system. This allows to evaluate the diffusion constant on the time--scale of the jump duration, which is small and temperature independent, well before the system enters the diffusive regime. The prediction is obtained by analyzing the particle trajectories via a parameter-free algorithm.

cond-mat.soft

Pacman Percolation and the Glass Transition

We investigate via Monte Carlo simulations the kinetically constrained Kob-Andersen lattice glass model showing that, contrary to current expectations, the relaxation process and the dynamical heterogeneities seems to be characterized by different time scales. Indeed, we found that the relaxation time is related to a reverse percolation transition, whereas the time of maximum heterogeneity is related to the spatial correlation between particles. This investigation leads to a geometrical interpretation of the relaxation processes and of the different observed time scales.

cond-mat.soft

'Flow & Jam' of frictional athermal systems under shear stress

We report recent results of molecular dynamics simulations of frictional athermal particles at constant volume fraction and constant applied shear stress, focusing on a range of control parameters where the system first flows, but then jams after a time tjam. On decreasing the volume fraction, the mean jamming time diverges, while its sample fluctuations become so large that the jamming time probability distribution P(tjam) becomes a power-law. We obtain an insight on the origin of this phenomenology focusing on the flowing regime, which is characterized by the presence of a clear correlation between the shear velocity and the mean number of contacts per particles Z, whereby small velocities occur when Z acquires higher values.

cond-mat.soft

Absence of `fragility' and mechanical response of jammed granular materials

We perform molecular dynamic (MD) simulations of frictional non-thermal particles driven by an externally applied shear stress. After the system jams following a transient flow, we probe its mechanical response in order to clarify whether the resulting solid is 'fragile'. We find the system to respond elastically and isotropically to small perturbations of the shear stress, suggesting absence of fragility. These results are interpreted in terms of the energy landscape of dissipative systems. For the same values of the control parameters, we check the behaviour of the system during a stress cycle. Increasing the maximum stress value, a crossover from a visco-elastic to a plastic regime is observed.

cond-mat.soft