arXiv subjects

Daniele Coslovich

Publications and source records attributed to Daniele Coslovich.

36 records · Page 2Linked to original sources

arXiv2016

Equilibrium sampling of hard spheres up to the jamming density and beyond

We implement and optimize a particle-swap Monte-Carlo algorithm that allows us to thermalize a polydisperse system of hard spheres up to unprecedentedly-large volume fractions, where \revise{previous} algorithms and experiments fail to equilibrate. We show that no glass singularity intervenes before the jamming density, which we independently determine through two distinct non-equilibrium protocols. We demonstrate that equilibrium fluid and non-equilibrium jammed states can have the same density, showing that the jamming transition cannot be the end-point of the fluid branch.

cond-mat.stat-mech↗

arXiv2016

Mean-field dynamic criticality and geometric transition in the Gaussian core model

We use molecular dynamics simulations to investigate dynamic heterogeneities and the potential energy landscape of the Gaussian core model (GCM). Despite the nearly Gaussian statistics of particles' displacements, the GCM exhibits giant dynamic heterogeneities close to the dynamic transition temperature. The divergence of the four-point susceptibility is quantitatively well described by the inhomogeneous version of the Mode-Coupling theory. Furthermore, the potential energy landscape of the GCM is characterized by a geometric transition and large energy barriers, as expected from the lack of activated, hopping dynamics. These observations demonstrate that all major features of mean-field dynamic criticality can be observed in a physically sound, three-dimensional model.

cond-mat.stat-mech↗

arXiv2015

Structure and dynamics of coupled viscous liquids

We perform Monte-Carlo simulations to analyse the structure and microscopic dynamics of a viscous Lennard-Jones liquid coupled to a quenched reference configuration of the same liquid. The coupling between the two replicas is introduced via a field epsilon conjugate to the overlap Q between the two particle configurations. This allows us to study the evolution of various static and dynamic correlation functions across the (epsilon, T) equilibrium phase diagram. As the temperature is decreased, we identify increasingly marked precursors of a first-order phase transition between a low-Q and a high-Q phase induced by the field epsilon. We show in particular that both static and dynamic susceptibilities have a maximum at a temperature-dependent value of the coupling field, which defines a `Widom line'. We also show that, in the high-overlap regime, diffusion and structural relaxation are strongly decoupled because single particle motion mostly occurs via discrete hopping on the sites defined by the reference configuration. These results, obtained using conventional numerical tools, provide encouraging signs that an equilibrium phase transition exists in coupled viscous liquids, but also demonstrate that important numerical challenges must be overcome to obtain more conclusive numerical evidence.

cond-mat.stat-mech↗

arXiv2015

Diverging viscosity and soft granular rheology in non-Brownian suspensions

We use large scale computer simulations and finite size scaling analysis to study the shear rheology of dense three-dimensional suspensions of frictionless non-Brownian particles in the vicinity of the jamming transition. We perform simulations of soft repulsive particles at constant shear rate, constant pressure, and finite system size, and study carefully the asymptotic limits of large system sizes and infinitely hard particle repulsion. Extending earlier analysis by about two orders of magnitude, we first study the asymptotic behavior of the shear viscosity in the hard particle limit. We confirm its asymptotic power law divergence at the jamming transition, but show that a precise determination of the critical density and critical exponent is difficult due to the `multiscaling' behavior of the viscosity. Additionally, finite-size scaling analysis suggests that this divergence is accompanied by a growing correlation length scale, which also diverges algebraically. We then study the effect of soft repulsion, and propose a natural extension of the standard granular rheology to account for softness effects, which we validate from simulations. Close to the jamming transition, this `soft granular rheology' offers a detailed description of the non-linear rheology of soft particles, which differs from earlier empirical scaling forms.

cond-mat.soft↗

arXiv2014

Correlation of Local Order with Particle Mobility in Supercooled Liquids is Highly System Dependent

We investigate the connection between local structure and dynamical heterogeneity in supercooled liquids. Through the study of four different models we show that the correlation between a particle's mobility and the degree of local order in nearby regions is highly system dependent. Our results suggest that the correlation between local structure and dynamics is weak or absent in systems that conform well to the mean-field picture of glassy dynamics and strong in those that deviate from this paradigm. Finally, we investigate the role of order-agnostic point-to-set correlations and reveal that they provide similar information content to local structure measures, at least in the system where local order is most pronounced.

cond-mat.stat-mech↗

arXiv2014

A novel approach to numerical measurements of the configurational entropy in supercooled liquids

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 entropy Sigma(T) in supercooled liquids, using a direct determination of the free energy cost to localize the system within a single metastable state at temperature T. For two prototypical glass-forming liquids, we find that Sigma(T) disappears discontinuously above a temperature T_c, which is slightly lower than the usual estimate of the onset temperature for glassy dynamics. This observation is in good agreement with theoretical expectations, but contrasts sharply with alternative numerical methods. While the temperature dependence of Sigma(T) correlates with the glass fragility, we show that the validity of the Adam-Gibbs relation (relating configurational entropy to structural relaxation time) established in earlier numerical studies is smaller than previously thought, potentially resolving an important conflict between experiments and simulations.

cond-mat.stat-mech↗

arXiv2014

Non-linear dynamic response of glass-forming liquids to random pinning

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 dynamic crossover at which the shape of the relaxing entities changes.

cond-mat.dis-nn↗

arXiv2013

Cluster and reentrant anomalies of nearly Gaussian core particles

We study through integral equation theory and numerical simulations the structure and dynamics of fluids composed of ultrasoft, nearly Gaussian particles. Namely, we explore the fluid phase diagram of a model in which particles interact via the generalized exponential potential u(r)=εexp[-(r/σ)^n], with a softness exponent n slightly larger than 2. In addition to the well-known anomaly associated to reentrant melting, the structure and dynamics of the fluid display two additional anomalies, which are visible in the isothermal variation of the structure factor and diffusivity. These features are correlated to the appearance of dimers in the fluid phase and to the subsequent modification of the cluster structure upon compression. We corroborate these results through an analysis of the local minima of the potential energy surface, in which clusters appear as much tighter conglomerates of particles. We find that reentrant melting and clustering coexist for softness exponents ranging from 2^+ up to values relevant for the description of amphiphilic dendrimers, i.e., n=3.

cond-mat.soft↗

arXiv2012

Static triplet correlations in glass-forming liquids: A molecular dynamics study

We present a numerical evaluation of the three-point static correlations functions of the Kob-Andersen Lennard-Jones binary mixture and of its purely repulsive, Weeks-Chandler-Andersen variant. In the glassy regime, the two models possess a similar pair structure, yet their dynamics differ markedly. The static triplet correlation functions S^(3) indicate that the local ordering is more pronounced in the Lennard-Jones model, an observation consistent with its slower dynamics. A comparison of the direct triplet correlation functions c^(3) reveals that these structural differences are due, to a good extent, to an amplification of the small discrepancies observed at the pair level. We demonstrate the existence of a broad, positive peak at small wave-vectors and angles in c^(3). In this portion of k-space, slight, systematic differences between the models are observed, revealing "genuine" three-body contributions to the triplet structure. The possible role of the low-k features of c^(3) and the implications of our results for dynamic theories of the glass transition are discussed.

cond-mat.stat-mech↗

arXiv2012

Finite size effects in the dynamics of glass-forming liquids

We present a comprehensive theoretical study of finite size effects in the relaxation dynamics of glass-forming liquids. Our analysis is motivated by recent theoretical progress regarding the understanding of relevant correlation length scales in liquids approaching the glass transition. We obtain predictions both from general theoretical arguments and from a variety of specific perspectives: mode-coupling theory, kinetically constrained and defect models, and random first order transition theory. In the latter approach, we predict in particular a non-monotonic evolution of finite size effects across the mode-coupling crossover due to the competition between mode-coupling and activated relaxation. We study the role of competing relaxation mechanisms in giving rise to non-monotonic finite size effects by devising a kinetically constrained model where the proximity to the mode-coupling singularity can be continuously tuned by changing the lattice topology. We use our theoretical findings to interpret the results of extensive molecular dynamics studies of four model liquids with distinct structures and kinetic fragilities. While the less fragile model only displays modest finite size effects, we find a more significant size dependence evolving with temperature for more fragile models, such as Lennard-Jones particles and soft spheres. Finally, for a binary mixture of harmonic spheres we observe the predicted non-monotonic temperature evolution of finite size effects near the fitted mode-coupling singularity, suggesting that the crossover from mode-coupling to activated dynamics is more pronounced for this model. Finally, we discuss the close connection between our results and the recent report of a non-monotonic temperature evolution of a dynamic length scale near the mode-coupling crossover in harmonic spheres.

cond-mat.stat-mech↗

arXiv2012

Cluster glasses of ultrasoft particles

We present molecular dynamics (MD) simulations results for dense fluids of ultrasoft, fully-penetrable particles. These are a binary mixture and a polydisperse system of particles interacting via the generalized exponential model, which is known to yield cluster crystal phases for the corresponding monodisperse systems. Because of the dispersity in the particle size, the systems investigated in this work do not crystallize and form disordered cluster phases. The clustering transition appears as a smooth crossover to a regime in which particles are mostly located in clusters, isolated particles being infrequent. The analysis of the internal cluster structure reveals microsegregation of the big and small particles, with a strong homo-coordination in the binary mixture. Upon further lowering the temperature below the clustering transition, the motion of the clusters' centers-of-mass slows down dramatically, giving way to a cluster glass transition. In the cluster glass, the diffusivities remain finite and display an activated temperature dependence, indicating that relaxation in the cluster glass occurs via particle hopping in a nearly arrested matrix of clusters. Finally we discuss the influence of the microscopic dynamics on the transport properties by comparing the MD results with Monte Carlo simulations.

cond-mat.soft↗

arXiv2011

Ultrasoft primitive model of polyionic solutions: structure, aggregation, and dynamics

We introduce an ultrasoft core model of interpenetrating polycations and polyanions with continuous Gaussian charge distributions, to investigate polyelectrolyte aggregation in dilute and semi-dilute, salt-free solutions. The model is studied by a combination of approximate theories (random phase approximation and hypernetted chain theory) and numerical simulations. The calculated pair structure, thermodynamics, phase diagram and polyion dynamics of the symmetric version of the model (the "ultrasoft restricted primitive model" or UPRM) differ from the corresponding properties of the widely studied "restricted primitive model" (RPM) where ions have hard cores. At sufficiently low temperatures and densities, oppositely charged polyions form weakly interacting, polarizable neutral pairs. The clustering probabilities, dielectric behavior and electrical conductivity point to a line of sharp conductor-insulator transitions in the density-temperature plane. At very low temperatures the conductor-insulator transition line terminates near the top of a first order coexistence curve separating a high-density, liquid phase from a low-density, vapor phase. The simulation data hint at a tricritical behavior, reminiscent of that observed of the two-dimensional Coulomb Gas, which contrasts with the Ising criticality of its three-dimensional counterpart, the RPM.

cond-mat.soft↗

arXiv2011

Dynamic arrest of colloids in porous environments: disentangling crowding and confinement

Using numerical simulations we study the slow dynamics of a colloidal hard-sphere fluid adsorbed in a matrix of disordered hard-sphere obstacles. We calculate separately the contributions to the single-particle dynamic correlation functions due to free and trapped particles. The separation is based on a Delaunay tessellation to partition the space accessible to the centres of fluid particles into percolating and disconnected voids. We find that the trapping of particles into disconnected voids of the matrix is responsible for the appearance of a nonzero long-time plateau in the single-particle intermediate scattering functions of the full fluid. The subdiffusive exponent $z$, obtained from the logarithmic derivative of the mean-squared displacement, is observed to be essentially unaffected by the motion of trapped particles: close to the percolation transition, we determined $z \simeq 0.5$ for both the full fluid and the particles moving in the percolating void. Notably, the same value of $z$ is found in single-file diffusion and is also predicted by mode-coupling theory along the diffusion-localisation line. We also reveal subtle effects of dynamic heterogeneity in both the free and the trapped component of the fluid particles, and discuss microscopic mechanisms that contribute to this phenomenon.

cond-mat.soft↗

arXiv2011

Locally preferred structures and many-body static correlations in viscous liquids

We investigate the influence of static correlations beyond the pair level on the dynamics of selected model glass-formers. We compare the pair structure, angular distribution functions, and statistics of Voronoi polyhedra of two well-known Lennard-Jones mixtures as well as of the corresponding Weeks-Chandler-Andersen variants, in which the attractive part of the potential is truncated. By means of the Voronoi construction we identify the atomic arrangements corresponding to the locally preferred structures of the models. We find that the growth of domains formed by interconnected locally preferred structures signals the onset of the slow dynamics regime and allows to rationalize the different dynamic behaviors of the models. At low temperature, the spatial extension of the structurally correlated domains, evaluated at fixed relaxation time, increases with the fragility of the models and is systematically reduced by truncating the attractions. In view of these results, proper inclusion of many-body static correlations in theories of the glass transition appears crucial for the description of the dynamics of fragile glass-formers.

cond-mat.stat-mech↗

arXiv2011

Clustering, conductor-insulator transition and phase separation of an ultrasoft model of electrolytes

We investigate the clustering and phase separation of a model of ultrasoft, oppositely charged macroions by a combination of Monte Carlo and Molecular Dynamics simulations. Static and dynamic diagnostics, including the dielectric permittivity and the electric conductivity of the model, show that ion pairing induces a sharp conductor-insulator transition at low temperatures and densities, which impacts the separation into dilute and concentrated phases below a critical temperature. Preliminary evidence is presented for a possible tricritical nature of the phase diagram of the model.

cond-mat.soft↗

arXiv2010

Hopping and microscopic dynamics of ultrasoft particles in cluster crystals

We have investigated the slow dynamics of ultrasoft particles in crystalline cluster phases, where point particles interact through the generalized exponential potential u(r) = ε\exp[-(r/σ)^n], focusing on the cluster fcc phase of this model with n=4. In an effort to elucidate how the mechanisms of mass transport depend on the microscopic dynamics and in order to mimic a realistic scenario in a related experiment we have performed molecular dynamics, Brownian dynamics, and Monte Carlo simulations. In molecular dynamics simulations the diffusion of particles proceeds through long-range jumps, guided by strong correlations in the momentum direction. In Monte Carlo and Brownian dynamics simulations jump events are short-ranged, reflecting the purely configurational nature of the dynamics. In contrast to what was found in models of glass-forming liquids, the effect of Newtonian and stochastic microscopic dynamics on the long-time relaxation cannot be accounted for by a temperature-independent rescaling of the time units. From the obvious qualitative discrepancies in the short time behavior between the three simulation methods and the non-trivial difference in jump length distributions, long time relaxation, and dynamic heterogeneity, we learn that a more complex modeling of the dynamics in realistic systems of ultrasoft colloids is required.

cond-mat.soft↗

arXiv2010

Impact of random obstacles on the dynamics of a dense colloidal fluid

Using molecular dynamics simulations we study the slow dynamics of a colloidal fluid annealed within a matrix of obstacles quenched from an equilibrated colloidal fluid. We choose all particles to be of the same size and to interact as hard spheres, thus retaining all features of the porous confinement while limiting the control parameters to the packing fraction of the matrix, Φm, and that of the fluid, Φf. We conduct detailed investigations on several dynamic properties, including the tagged-particle and collective intermediate scattering functions, the mean-squared displacement, and the van Hove function. We show the confining obstacles to profoundly impact the relaxation pattern of various quantifiers pertinent to the fluid. Varying the type of quantifier (tagged-particle or collective) as well as Φm and Φf, we unveil both discontinuous and continuous arrest scenarios. Furthermore, we discover subdiffusive behavior and demonstrate its close connection to the matrix structure. Our findings partly confirm the various predictions of a recent extension of mode-coupling theory to the quenched-annealed protocol.

cond-mat.soft↗

arXiv2009

Single-particle and collective slow dynamics of colloids in porous confinement

Using molecular dynamics simulations we study the slow dynamics of a hard sphere fluid confined in a disordered porous matrix. The presence of both discontinuous and continuous glass transitions as well as the complex interplay between single-particle and collective dynamics are well captured by a recent extension of mode-coupling theory for fluids in porous media. The degree of universality of the mode-coupling theory predictions for related models of colloids is studied by introducing size-disparity between fluid and matrix particles, as well as softness in the interactions.

cond-mat.soft↗