arXiv subjects

Francesco Sciortino

Publications and source records attributed to Francesco Sciortino.

At least 109 records · Page 6Linked to original sources

arXiv2009

Connecting Irreversible to Reversible Aggregation: Time and Temperature

We report molecular dynamics simulations of a gel-forming mixture of ellipsoidal patchy particles with different functionality. We show that in this model, which disfavors the formation of bond-loops, elapsed time during irreversible aggregation -- leading to the formation of an extended network -- can be formally correlated with equilibrium temperature in reversible aggregation. We also show that it is possible to develop a parameter-free description of the self-assembly kinetics, bringing reversible and irreversible aggregation of loopless branched systems to the same level of understanding as equilibrium polymerization.

cond-mat.dis-nn↗

arXiv2008

Multiple glass transitions in star polymer mixtures: Insights from theory and simulations

The glass transition in binary mixtures of star polymers is studied by mode coupling theory and extensive molecular dynamics computer simulations. In particular, we have explored vitrification in the parameter space of size asymmetry $δ$ and concentration $ρ_2$ of the small star polymers at fixed concentration of the large ones. Depending on the choice of parameters, three different glassy states are identified: a single glass of big polymers at low $δ$ and low $ρ_2$, a double glass at high $δ$ and low $ρ_2$, and a novel double glass at high $ρ_2$ and high $δ$ which is characterized by a strong localization of the small particles. At low $δ$ and high $ρ_2$ there is a competition between vitrification and phase separation. Centered in the $(δ, ρ_2)$-plane, a liquid lake shows up revealing reentrant glass formation. We compare the behavior of the dynamical density correlators with the predictions of the theory and find remarkable agreement between the two.

cond-mat.soft↗

arXiv2008

Gelation as arrested phase separation in short-ranged attractive colloid-polymer mixtures

We present further evidence that gelation is an arrested phase separation in attractive colloid-polymer mixtures, based on a method combining confocal microscopy experiments with numerical simulations recently established in {\bf Nature 453, 499 (2008)}. Our results are independent of the form of the interparticle attractive potential, and therefore should apply broadly to any attractive particle system with short-ranged, isotropic attractions. We also give additional characterization of the gel states in terms of their structure, inhomogeneous character and local density.

cond-mat.soft↗

arXiv2008

Hierarchies of networked phases induced by multiple liquid-liquid critical points

Functionalization of nanoparticles or colloids is increasingly being used to develop customizable "atoms". Functionalization by attaching single strands of DNA allows for direct control of the binding between nanoparticles, since hybridization of double strands will only occur if the base sequences of single strands are complementary. Nanoparticles and colloids functionalized by four single strands of DNA can be thought of as designed analogs to tetrahedral network forming atoms and molecules, with a difference that the attached DNA strands allow for control of the length scale of bonding relative to the core size. We explore the behavior of an experimentally realized model for a nanoparticles functionalized by four single strands of DNA (a tetramer), and show that this single-component model exhibits a rich phase diagram with at least three critical points and four thermodynamically distinct amorphous phases. We demonstrate that the additional critical points are part of the Ising universality class, like the ordinary liquid-gas critical point. The dense phases consist of a hierarchy of interpenetrating networks, reminiscent of a woven cloth. Thus bonding specificity of DNA provides an effective route to generate new nano-networked materials with polyamorphic behavior. The concept of network interpenetration helps to explain the generation of multiple liquid phases in single-component systems, suggested to occur in some atomic and molecular network forming fluids, including water and silica.

cond-mat.soft↗

arXiv2008

Numerical Investigation of Glassy Dynamics in Low Density Systems

Vitrification in colloidal systems typically occurs at high densities driven by sharply varying, short-ranged interactions. The possibility of glassy behavior arising from smoothly varying, long-ranged particle interactions has received relatively little attention. Here we investigate the behavior of screened charged particles, and explicitly demonstrate that these systems exhibit glassy properties in the regime of low temperature and low density. Properties close to this low density (Wigner) glass transition share many features with their hard-sphere counterparts, but differ in quantitative aspects that may be accounted for via microscopic theoretical considerations.

cond-mat.dis-nn↗

arXiv2008

A molecular dynamics study of chemical gelation in a patchy particle model

We report event-driven molecular dynamics simulations of the irreversible gelation of hard ellipsoids of revolution containing several associating groups, characterizing how the cluster size distribution evolves as a function of the extent of reaction, both below and above the gel point. We find that in a very large interval of values of the extent of reaction, parameter-free mean-field predictions are extremely accurate, providing evidence that in this model the Ginzburg zone near the gel point, where non-mean field effects are important, is very limited. We also find that the Flory's hypothesis for the post-gelation regime properly describes the connectivity of the clusters even if the long-time limit of the extent of reaction does not reach the fully reacted state. This study shows that irreversibly aggregating asymmetric hard-core patchy particles may provide a close realization of the mean-field model, for which available theoretical predictions may help control the structure and the connectivity of the gel state. Besides chemical gels, the model is relevant to network-forming soft materials like systems with bioselective interactions, functionalized molecules and patchy colloids.

cond-mat.soft↗

arXiv2008

Theoretical and numerical study of the phase diagram of patchy colloids: ordered and disordered patch arrangements

We report theoretical and numerical evaluations of the phase diagram for a model of patchy particles. Specifically we study hard-spheres whose surface is decorated by a small number f of identical sites ("sticky spots'') interacting via a short-range square-well attraction. We theoretically evaluate, solving the Wertheim theory, the location of the critical point and the gas-liquid coexistence line for several values of f and compare them to results of Gibbs and Grand Canonical Monte Carlo simulations. We study both ordered and disordered arrangements of the sites on the hard-sphere surface and confirm that patchiness has a strong effect on the phase diagram: the gas-liquid coexistence region in the temperature-density plane is significantly reduced as f decreases. We also theoretically evaluate the locus of specific heat maxima and the percolation line.

cond-mat.soft↗

arXiv2007

Event-Driven Simulation of the Dynamics of Hard Ellipsoids

We introduce a novel algorithm to perform event-driven simulations of hard rigid bodies of arbitrary shape, that relies on the evaluation of the geometric distance. In the case of a monodisperse system of uniaxial hard ellipsoids,we perform molecular dynamics simulations varying the aspect-ratio X0 and the packing fraction phi. We evaluate the translational Dtrans and the rotational Drot diffusion coefficient and the associated isodiffusivity lines in the phi-X0 plane. We observe a decoupling of the translational and rotational dynamics which generates an almost perpendicular crossing of the Dtrans and Drot isodiffusivity lines. While the self intermediate scattering function exhibits stretched relaxation, i.e. glassy dynamics, only for large phi and X0 about equals to 1, the second order orientational correlator C2(t) shows stretching only for large and small X0 values. We discuss these findings in the context of a possible pre-nematic order driven glass transition.

cond-mat.soft↗

arXiv2007

Gel-forming patchy colloids and network glass formers: Thermodynamic and Dynamic analogies

This article discusses recent attempts to provide a deeper understanding of the thermoreversible "gel" state of colloidal matter and to unravel the analogies between gels at the colloidal level and gels at the molecular level, commonly known as network-forming strong liquids. The connection between gel-forming patchy colloids and strong liquids is provided by the limited valence of the inter-particle interactions, i.e. by the presence of a limit in the number of bonded nearest neighbors.

cond-mat.soft↗

arXiv2007

A fully solvable equilibrium self-assembly process: fine tuning the clusters size and the connectivity in patchy particle systems

Self-assembly is the mechanism that controls the formation of well defined structures from disordered pre-existing parts. Despite the importance of self-assembly as a manufacturing method and the increasingly large number of experimental realizations of complex self-assembled nano aggregates, theoretical predictions are lagging behind. Here we show that for a non-trivial self-assembly phenomenon, originating branched loop-less clusters, it is possible to derive a fully predictive parameter-free theory of equilibrium self-assembly by combining the Wertheim theory for associating liquids with the Flory-Stockmayer approach for chemical gelation.

cond-mat.soft↗

arXiv2007

A spherical model with directional interactions: I. Static properties

We introduce a simple spherical model whose structural properties are similar to the ones generated by models with directional interactions, by employing a binary mixture of large and small hard spheres, with a square-well attraction acting only between particles of different size. The small particles provide the bonds between the large ones. With a proper choice of the interaction parameters, as well as of the relative concentration of the two species, it is possible to control the effective valence. Here we focus on a specific choice of the parameters which favors tetrahedral ordering and study the equilibrium static properties of the system in a large window of densities and temperatures. Upon lowering the temperature we observe a progressive increase in local order, accompanied by the formation of a four-coordinated network of bonds. Three different density regions are observed: at low density the system phase separates into a gas and a liquid phase; at intermediate densities a network of fully bonded particles develops; at high densities -- due to the competition between excluded volume and attractive interactions -- the system forms a defective network. The very same behavior has been previously observed in numerical studies of non-spherical models for molecular liquids, such as water, and in models of patchy colloidal particles. Differently from these models, theoretical treatments devised for spherical potentials, e.g. integral equations and ideal mode coupling theory for the glass transition can be applied in the present case, opening the way for a deeper understanding of the thermodynamic and dynamic behavior of low valence molecules and particles.

cond-mat.dis-nn↗

arXiv2007

On the possibility of extending the Nore-Frenkel generalized law of correspondent states to non-isotropic patchy interactions

Colloidal systems (and protein solutions) are often characterized by attractive interactions whose range is much smaller than the particle size. When this is the case and the interaction is spherical, systems obey a generalized law of correspondent states (GLCS), first proposed by Noro and Frenkel [ J.Chem.Phys. 113, 2941 (2000) ]. The thermodynamic properties become insensitive to the details of the potential, depending only on the value of the second virial coefficient B_2 and the density $ρ$. The GLCS does not generically hold for the case of non-spherical potentials. In this Letter we suggest that when particles interact via short-ranged small-angular amplitude patchy interactions (so that the condition of only one bond per patch is fulfilled) it is still possible to generalize the GLCS close to the liquid-gas critical point. Keywords: Colloids, Second Virial Coefficient, Proteins interactions, Short-ranged attractive attractions.

cond-mat.soft↗

arXiv2007

Viscoelasticity and Stokes-Einstein relation in repulsive and attractive colloidal glasses

We report a numerical investigation of the visco-elastic behavior in models for steric repulsive and short-range attractive colloidal suspensions, along different paths in the attraction-strength vs packing fraction plane. More specifically, we study the behavior of the viscosity (and its frequency dependence) on approaching the repulsive glass, the attractive glass and in the re-entrant region where viscosity shows a non monotonic behavior on increasing attraction strength. On approaching the glass lines, the increase of the viscosity is consistent with a power-law divergence with the same exponent and critical packing fraction previously obtained for the divergence of the density fluctuations. Based on mode-coupling calculations, we associate the increase of the viscosity with specific contributions from different length scales. We also show that the results are independent on the microscopic dynamics by comparing newtonian and brownian simulations for the same model. Finally we evaluate the Stokes-Einstein relation approaching both glass transitions, finding a clear breakdown which is particularly strong for the case of the attractive glass.

cond-mat.soft↗

arXiv2007

Effective non-additive pair potential for lock-and-key interacting particles: the role of the limited valence

Theoretical studies of self-assembly processes and condensed phases in colloidal systems are often based on effective inter-particle potentials. Here we show that developing an effective potential for particles interacting with a limited number of ``lock-and-key'' selective bonds (due to the specificity of bio-molecular interactions) requires -- beside the non-sphericity of the potential -- a (many body) constraint that prevent multiple bonding on the same site. We show the importance of retaining both valence and bond-selectivity by developing, as a case study, a simple effective potential describing the interaction between colloidal particles coated by four single-strand DNA chains.

cond-mat.soft↗

arXiv2007

Metabasin dynamics and local structure in supercooled water

We employ the Distance Matrix method to investigate metabasin dynamics in supercooled water. We find that the motion of the system consists in the exploration of a finite region of configuration space (enclosing several distinct local minima), named metabasin, followed by a sharp crossing to a different metabasin. The characteristic time between metabasin transitions is comparable to the structural relaxation time, suggesting that these transitions are relevant for the long time dynamics. The crossing between metabasins is accompanied by very rapid diffusional jumps of several groups of dynamically correlated particles. These particles form relatively compact clusters and act as cooperative relaxing units responsible for the density relaxation. We find that these mobile particles are often characterized by an average coordination larger than four, i.e. are located in regions where the tetrahedral hydrogen bond network is distorted.

cond-mat.soft↗

arXiv2006

Phase diagram of patchy colloids: towards empty liquids

We report theoretical and numerical evaluations of the phase diagram for patchy colloidal particles of new generation. We show that the reduction of the number of bonded nearest neighbours offers the possibility of generating liquid states (i.e. states with temperature $T$ lower than the liquid-gas critical temperature) with a vanishing occupied packing fraction ($ϕ$), a case which can not be realized with spherically interacting particles. Theoretical results suggest that such reduction is accompanied by an increase of the region of stability of the liquid phase in the ($T$-$ϕ$) plane, possibly favoring the establishment of homogeneous disordered materials at small $ϕ$, i.e. stable equilibrium gels.

cond-mat.soft↗

arXiv2006

Maximum Valency Lattice Gas Models

We study lattice gas models with the imposition of a constraint on the maximum number of bonds (nearest neighbor interactions) that particles can participate in. The critical parameters, as well as the coexistence region are studied using the mean field approximation and the Bethe-Peierls approximation. We find that the reduction of the number of interactions suppresses the temperature-density region where the liquid and gas phases coexist. We confirm these results from simulations using the histogram reweighting method employing grand Canonical Monte Carlo simulations.

cond-mat.soft↗

arXiv2006

Modeling Equilibrium Clusters in Lysozyme Solutions

We present a combined experimental and numerical study of the equilibrium cluster formation in globular protein solutions under no-added salt conditions. We show that a cluster phase emerges as a result of a competition between a long-range screened Coulomb repulsion and a short-range attraction. A simple effective potential, in which only depth and width of the attractive part of the potential are optimized, accounts in a remarkable way for the wavevector dependence of the X-ray scattering structure factor.

cond-mat.soft↗