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E Zaccarelli

Publications and source records attributed to E Zaccarelli.

17 recordsLinked to original sources
PubMed2006

Non-Gaussian energy landscape of a simple model for strong network-forming liquids: Accurate evaluation of the configurational entropy.

We present a numerical study of the statistical properties of the potential energy landscape of a simple model for strong network-forming liquids. The model is a system of spherical particles interacting through a square-well potential, with an additional constraint that limits the maximum number of bonds Nmax per particle. Extensive simulations have been carried out as a function of temperature, packing fraction, and Nmax. The dynamics of this model are characterized by Arrhenius temperature dependence of the transport coefficients and by nearly exponential relaxation of dynamic correlators, i.e., features defining strong glass-forming liquids. This model has two important features: (i) Landscape basins can be associated with bonding patterns. (ii) The configurational volume of the basin can be evaluated in a formally exact way, and numerically with an arbitrary precision. These features allow us to evaluate the number of different topologies the bonding pattern can adopt. We find that the number of fully bonded configurations, i.e., configurations in which all particles are bonded to Nmax neighbors, is extensive, suggesting that the configurational entropy of the low temperature fluid is finite. We also evaluate the energy dependence of the configurational entropy close to the fully bonded state and show that it follows a logarithmic functional form, different from the quadratic dependence characterizing fragile liquids. We suggest that the presence of a discrete energy scale, provided by the particle bonds, and the intrinsic degeneracy of fully bonded disordered networks differentiates strong from fragile behavior.

Journal Article↗
PubMed2006

Gel to glass transition in simulation of a valence-limited colloidal system.

We numerically study a simple model for thermoreversible colloidal gelation in which particles can form reversible bonds with a predefined maximum number of neighbors. We focus on three and four maximally coordinated particles, since in these two cases the low valency makes it possible to probe, in equilibrium, slow dynamics down to very low temperatures T. By studying a large region of T and packing fraction phi we are able to estimate both the location of the liquid-gas phase separation spinodal and the locus of dynamic arrest, where the system is trapped in a disordered nonergodic state. We find that there are two distinct arrest lines for the system: a glass line at high packing fraction, and a gel line at low phi and T. The former is rather vertical (phi controlled), while the latter is rather horizontal (T controlled) in the phi-T plane. Dynamics on approaching the glass line along isotherms exhibit a power-law dependence on phi, while dynamics along isochores follow an activated (Arrhenius) dependence. The gel has clearly distinct properties from those of both a repulsive and an attractive glass. A gel to glass crossover occurs in a fairly narrow range in phi along low-T isotherms, seen most strikingly in the behavior of the nonergodicity factor. Interestingly, we detect the presence of anomalous dynamics, such as subdiffusive behavior for the mean squared displacement and logarithmic decay for the density correlation functions in the region where the gel dynamics interferes with the glass dynamics.

Journal Article↗
PubMed2005

Tailoring the flow of soft glasses by soft additives.

We examine the vitrification and melting of asymmetric star polymer mixtures by combining rheological measurements with mode coupling theory. We identify two types of glassy states, a single glass, in which the small component is fluid in the glassy matrix of the big one, and a double glass, in which both components are vitrified. Addition of small-star polymers leads to melting of both glasses, and the melting curve has a nonmonotonic dependence on the star-star size ratio. The phenomenon opens new ways for externally steering the rheological behavior of soft matter systems.

Computer Simulation↗
PubMed2005

One-dimensional cluster growth and branching gels in colloidal systems with short-range depletion attraction and screened electrostatic repulsion.

We report extensive numerical simulations of a simple model for charged colloidal particles in suspension with small nonadsorbing polymers. The chosen effective one-component interaction potential is composed of a short-range attractive part complemented by a Yukawa repulsive tail. We focus on the case where the screening length is comparable to the particle radius. Under these conditions, at low temperature, particles locally cluster into quasi one-dimensional aggregates which, via a branching mechanism, form a macroscopic percolating gel structure. We discuss gel formation and contrast it with the case of longer screening lengths, for which previous studies have shown that arrest is driven by the approach to a Yukawa glass of spherical clusters. We compare our results with recent experimental work on charged colloidal suspensions (Phys. Rev. Lett. 2005, 94, 208301).

Journal Article↗
PubMed2005

Energy landscape of a simple model for strong liquids.

We calculate the statistical properties of the energy landscape of a minimal model for strong network-forming liquids. Dynamic and thermodynamic properties of this model can be computed with arbitrary precision even at low temperatures. A degenerate disordered ground state and logarithmic statistics for the local minima energy distribution are the landscape signatures of strong liquid behavior. Differences from fragile liquid properties are attributed to the presence of a discrete energy scale, provided by the particle bonds, and to the intrinsic degeneracy of topologically disordered networks.

Complex Mixtures↗
PubMed2005

Model for reversible colloidal gelation.

We report a numerical study, covering a wide range of packing fraction Phi and temperature T, for a system of particles interacting via a square well potential supplemented by an additional constraint on the maximum number n(max) of bonded interactions. We show that, when n(max)<6, the liquid-gas coexistence region shrinks, giving access to regions of low Phi where dynamics can be followed down to low T without an intervening phase separation. We characterize these arrested states at low densities (gel states) in terms of structure and dynamical slowing down, pointing out features which are very different from the standard glassy states observed at high Phi values.

Biophysics↗
PubMed2005

Starlike micelles with starlike interactions: a quantitative evaluation of structure factors and phase diagram.

Starlike PEP-PEO block copolymer micelles offer the possibility to investigate the phase behavior and interactions of regular star polymers (ultrasoft colloids). Micellar functionality f can be smoothly varied by changing solvent composition (interfacial tension). Structure factors obtained by small-angle neutron-scattering can be quantitatively described in terms of an effective potential for star polymers. The experimental phase diagram reproduces to a high level of accuracy the predicted liquid-solid transition. Whereas for intermediate f a bcc phase is observed, for high f the formation of a fcc phase is preempted by glass formation.

Journal Article↗
PubMed2004

Ground-state clusters for short-range attractive and long-range repulsive potentials.

We report calculations of the ground-state energies and geometries for clusters of different sizes (up to 80 particles), where individual particles interact simultaneously via a short-ranged attractive potential, modeled with a generalization of the Lennard-Jones potential, and a long-ranged repulsive Yukawa potential. We show that for specific choices of the parameters of the repulsive potential, the ground-state energy per particle has a minimum at a finite cluster size. For these values of the parameters in the thermodynamic limit, at low temperatures and small packing fractions, where clustering is favored and cluster-cluster interactions can be neglected, thermodynamically stable cluster phases can be formed. The analysis of the ground-state geometries shows that the spherical shape is marginally stable. In the majority of the studied cases, we find that above a certain size, ground-state clusters preferentially grow almost in one dimension.

Models, Chemical↗
PubMed2004

Effect of bond lifetime on the dynamics of a short-range attractive colloidal system.

We perform molecular dynamics simulations of short-range attractive colloid particles modeled by a narrow (3% of the hard sphere diameter) square well potential of unit depth. We compare the dynamics of systems with the same thermodynamics but different bond lifetimes, by adding to the square well potential a thin barrier at the edge of the attractive well. For permanent bonds, the relaxation time tau diverges as the packing fraction phi approaches a threshold related to percolation, while for short-lived bonds, the phi dependence of tau is more typical of a glassy system. At intermediate bond lifetimes, the phi dependence of tau is driven by percolation at low phi , but then crosses over to glassy behavior at higher phi . We also study the wave vector dependence of the percolation dynamics.

Journal Article↗
PubMed2004

Is there a reentrant glass in binary mixtures?

By employing computer simulations for a model binary mixture, we show that a reentrant glass transition upon adding a second component occurs only if the ratio alpha of the short-time mobilities between the glass-forming component and the additive is sufficiently small. For alpha approximately 1, there is no reentrant glass, even if the size asymmetry between the two components is large, in accordance with the two-component mode-coupling theory. For alpha<<1, on the other hand, the reentrant glass is observed and reproduced only by an effective one-component mode-coupling theory.

Journal Article↗
PubMed2004

Aging in short-ranged attractive colloids: a numerical study.

We study the aging dynamics in a model for dense simple liquids, in which particles interact through a hard-core repulsion complemented by a short-ranged attractive potential, of the kind found in colloidal suspensions. In this system, at large packing fractions, kinetically arrested disordered states can be created both on cooling (attractive glass) and on heating (repulsive glass). The possibility of having two distinct glasses, at the same packing fraction, with two different dynamics offers the unique possibility of comparing-within the same model-the differences in aging dynamics. We find that, while the aging dynamics of the repulsive glass is similar to the one observed in atomic and molecular systems, the aging dynamics of the attractive glass shows novel unexpected features.

Journal Article↗
PubMed2003

Structural arrest in dense star-polymer solutions.

The dynamics of star polymers is investigated via extensive molecular and Brownian dynamics simulations for a large range of functionality f and packing fraction eta. The calculated isodiffusivity curves display both minima and maxima as a function of eta and minima as a function of f. Simulation results are compared with theoretical predictions based on different approximations for the structure factor. In particular, the ideal glass transition line predicted by mode-coupling theory is shown to exactly track the isodiffusivity curves, offering a theoretical understanding for the observation of disordered arrested states in star-polymer solutions.

Journal Article↗
PubMed2002

Confirmation of anomalous dynamical arrest in attractive colloids: a molecular dynamics study.

Previous theoretical simulation and experimental studies have indicated that particles with a short-ranged attraction exhibit a range of dynamical arrest phenomena. These include very pronounced reentrance in the dynamical arrest curve, a logarithmic singularity in the density correlation functions, and the existence of "attractive" and "repulsive" glasses. Here we carry out extensive molecular dynamics calculations on dense systems interacting via a square-well potential. This is one of the simplest systems with the required properties, and may be regarded as canonical for interpreting the phase diagram, and now also the dynamical arrest. We confirm the theoretical predictions for reentrance, logarithmic singularity, and give a direct evidence of the existence, independent of theory, of two distinct glasses. We now regard the previous predictions of these phenomena as having been established.

Journal Article↗
PubMed2002

Evidence for an unusual dynamical-arrest scenario in short-ranged colloidal systems.

Extensive molecular dynamics simulation studies of particles interacting via a short-ranged attractive square-well potential are reported. The calculated loci of constant diffusion coefficient D in the temperature-packing fraction plane show a reentrant behavior, i.e., an increase of diffusivity on cooling, confirming an important part of the high volume-fraction dynamical-arrest scenario earlier predicted by theory for particles with short-ranged potentials. The more efficient localization mechanism induced by the short-range bonding provides, on average, additional free volume as compared to the hard-sphere case and results in faster dynamics.

Journal Article↗
PubMed2001

Mechanical properties of a model of attractive colloidal solutions.

We review the nature of glass transitions and the glasses arising from a square-well potential with a narrow and deep well. Our discussion is based on the mode coupling theory (MCT), and the predictions of glasses that we make refer to the "ideal" glasses predicted by this theory. We believe that the square-well system well represents colloidal particles with attractive interactions produced by grafted polymers, or depletion interactions. It has been recently shown that two types of glasses, an attractive and a repulsive one, are predicted by MCT for this model. The former can form at quite low densities. Most of our attention is directed at the mechanical properties of the glasses predicted by this theory. In particular we calculate the elastic shear modulus at zero frequency and the longitudinal stress modulus in the long wavelength limit. Results for both are presented along the glass-liquid transition curves and their interesting behavior is explained in terms of the underlying physics of the system.

Journal Article↗
PubMed2000

Higher-order glass-transition singularities in colloidal systems with attractive interactions.

The transition from a liquid to a glass in colloidal suspensions of particles interacting through a hard core plus an attractive square-well potential is studied within the mode-coupling-theory framework. When the width of the attractive potential is much shorter than the hard-core diameter, a reentrant behavior of the liquid-glass line and a glass-glass-transition line are found in the temperature-density plane of the model. For small well-width values, the glass-glass-transition line terminates in a third-order bifurcation point, i.e., in a A3 (cusp) singularity. On increasing the square-well width, the glass-glass line disappears, giving rise to a fourth-order A4 (swallow-tail) singularity at a critical well width. Close to the A3 and A4 singularities the decay of the density correlators shows stretching of huge dynamical windows, in particular logarithmic time dependence.

Journal Article↗