arXiv subjects

Francesco Sciortino

Publications and source records attributed to Francesco Sciortino.

At least 91 records · Page 5Linked to original sources

arXiv2012

Tuning effective interactions close to the critical point in colloidal suspensions

We report a numerical investigation of two colloids immersed in a critical solvent, with the aim of quantifying the effective colloid-colloid interaction potential. By turning on an attraction between the colloid and the solvent particles we follow the evolution from the case in which the solvent density close to the colloids changes from values smaller than the bulk to values larger than the bulk. We thus effectively implement the so-called $(+,+)$ and $(-,-)$ boundary conditions defined in field theoretical approaches focused on the description of critical Casimir forces. We find that the effective potential at large distances decays exponentially, with a characteristic decay length compatible with the bulk critical correlation length, in full agreement with theoretical predictions. We also investigate the case of $(+,-)$ boundary condition, where the effective potential becomes repulsive. Our study provides a guidance for a design of the interaction potential which can be exploited to control the stability of colloidal systems.

cond-mat.soft↗

arXiv2012

Properties of patchy colloidal particles close to a surface: a Monte Carlo and density functional study

We investigate the behavior of a patchy particle model close to a hard-wall via Monte Carlo simulation and density functional theory (DFT). Two DFT approaches, based on the homogeneous and inhomogeneous versions of Wertheim's first order perturbation theory for the association free energy are used. We evaluate, by simulation and theory, the equilibrium bulk phase diagram of the fluid and analyze the surface properties for two isochores, one of which is close to the liquid side of the gas-liquid coexistence curve. We find that the density profile near the wall crosses over from a typical high-temperature adsorption profile to a low-temperature desorption one, for the isochore close to coexistence. We relate this behavior to the properties of the bulk network liquid and find that the theoretical descriptions are reasonably accurate in this regime. At very low temperatures, however, an almost fully bonded network is formed, and the simulations reveal a second adsorption regime which is not captured by DFT. We trace this failure to the neglect of orientational correlations of the particles, which are found to exhibit surface induced orientational order in this regime.

cond-mat.soft↗

arXiv2012

Self-assembly of short DNA duplexes: from a coarse-grained model to experiments through a theoretical link

Short blunt-ended DNA duplexes comprising 6 to 20 base pairs self-assemble into polydisperse semi-flexible chains due to hydrophobic stacking interactions between terminal base pairs. Above a critical concentration, which depends on temperature and duplex length, such chains order into liquid crystal phases. Here, we investigate the self-assembly of such double-helical duplexes with a combined numerical and theoretical approach. We simulate the bulk system employing the coarse-grained DNA model recently proposed by Ouldridge et al. [ J. Chem. Phys. 134, 08501 (2011) ]. Then we evaluate the input quantities for the theoretical framework directly from the DNA model. The resulting parameter-free theoretical predictions provide an accurate description of the simulation results in the isotropic phase. In addition, the theoretical isotropic-nematic phase boundaries are in line with experimental findings, providing a route to estimate the stacking free energy.

cond-mat.soft↗

arXiv2012

Fluid-Fluid and Fluid-Solid transitions in the Kern-Frenkel model from Barker-Henderson thermodynamic perturbation theory

We study the Kern-Frenkel model for patchy colloids using Barker-Henderson second-order thermodynamic perturbation theory. The model describes a fluid where hard sphere particles are decorated with one patch, so that they interact via a square-well (SW) potential if they are sufficiently close one another, and if patches on each particle are properly aligned. Both the gas-liquid and fluid-solid phase coexistences are computed and contrasted against corresponding Monte-Carlo simulations results. We find that the perturbation theory describes rather accurately numerical simulations all the way from a fully covered square-well potential down to the Janus limit (half coverage). In the region where numerical data are not available (from Janus to hard-spheres), the method provides estimates of the location of the critical lines that could serve as a guideline for further efficient numerical work at these low coverages. A comparison with other techniques, such as integral equation theory, highlights the important aspect of this methodology in the present context.

cond-mat.soft↗

arXiv2011

Self-assembly of bi-functional patchy particles with anisotropic shape into polymers chains: theory and simulations

Concentrated solutions of short blunt-ended DNA duplexes, down to 6 base pairs, are known to order into the nematic liquid crystal phase. This self-assembly is due to the stacking interactions between the duplex terminals that promotes their aggregation into poly-disperse chains with a significant persistence length. Experiments show that liquid crystals phases form above a critical volume fraction depending on the duplex length. We introduce and investigate via numerical simulations, a coarse-grained model of DNA double-helical duplexes. Each duplex is represented as an hard quasi-cylinder whose bases are decorated with two identical reactive sites. The stacking interaction between terminal sites is modeled via a short-range square-well potential. We compare the numerical results with predictions based on a free energy functional and find satisfactory quantitative matching of the isotropic-nematic phase boundary and of the system structure. Comparison of numerical and theoretical results with experimental findings confirm that the DNA duplexes self-assembly can be properly modeled via equilibrium polymerization of cylindrical particles and enables us to estimate the stacking energy.

cond-mat.soft↗

arXiv2011

The vibrational density of states of a disordered gel model

We investigate the vibrational density of states (vDOS) in harmonic approximation of a binary mixture of colloidal patchy particles with two and three patches for different relative compositions $x_2$. At low temperature, this system forms a thermo-reversible gel, i.e. a fully bonded network of chains of two-patches particles, in which the branching points are provided by three-patches particles. For all the compositions we find in the vDOS a pronounced peak at low frequency whose height grows on increasing the fraction of two-functional particles, or equivalently with the average length of the chains. To identify the various spectral features, we compare the vDOS of the whole system with the one of small representative structures of the network and with the vDOS of a long linear chain of two-patches particles and we find that these structures are indeed able to rationalize the various peaks in the vDOS of the full system. At large $x_2$ the vDOS of the gel and of the long chain show remarkable similarities. Analyzing the dispersion relations and the spectrum of the linear chain we show that the excess of low frequency modes, the analog of the boson peak in glassy disordered systems, arises from the strong coupling between rotations and translations.

cond-mat.soft↗

arXiv2011

Nucleation barriers in tetrahedral liquids spanning glassy and crystallizing regimes

Crystallization and vitrification of tetrahedral liquids are important both from a fundamental and a technological point of view. Here, we study via extensive umbrella sampling Monte Carlo computer simulations the nucleation barriers for a simple model for tetrahedral patchy particles in the regime where open tetrahedral crystal structures (namely cubic and hexagonal diamond and their stacking hybrids) are thermodynamically stable. We show that by changing the angular bond width, it is possible to move from a glass-forming model to a readily crystallizing model. From the shape of the barrier we infer the role of surface tension in the formation of the crystalline clusters. Studying the trends of the nucleation barriers with the temperature and the patch width, we are able to identify an optimal value of the patch size that leads to easy nucleation. Finally, we find that the nucleation barrier is the same, within our numerical precision, for both diamond crystals and for their stacking forms.

cond-mat.soft↗

arXiv2011

Dynamical Behavior Near a Liquid-Liquid Phase Transition in Simulations of Supercooled Water

We examine the behavior of the diffusion coefficient of the ST2 model of water over a broad region of the phase diagram via molecular dynamics simulations. The ST2 model has an accessible liquid-liquid transition between low-density and high-density phases, making the model an ideal candidate to explore the impacts of the liquid-liquid transition on dynamics. We locate characteristic dynamical loci in the phase diagram and compare them with the previously investigated thermodynamic loci. The low-density liquid phase shows a crossover from non-Arrhenius to Arrhenius behavior, signaling the onset of a crossover from fragile-to-strong behavior. We explain this crossover in terms of the asymptotic approach of the low-density liquid to a random tetrahedral network, and show that the temperature dependence of the diffusion coefficient over a wide temperature range can be simply related to the concentration of defects in the network. Our findings thus confirm that the low-density phase of ST2 water is a well-defined metastable liquid.

cond-mat.stat-mech↗

arXiv2011

Crystal phases of two dimensional assembly of triblock Janus particles

Recent experimental work on spherical colloidal particles decorated with two hydrophobic poles separated by an electrically-charged middle band (triblock Janus particles) has documented self-assembly into a Kagome two-dimensional lattice, when particles are confined by gravity at the bottom of the sample holder [Q. Chen {\em et. al.}, Nature, in press]. Here we assess the ability of a previously proposed simple two-patch effective potential to reproduce the experimental findings. We show that the effective potential is able to reproduce the observed crystallization pathway in the Kagome structure. Based on free energy calculations, we also show that the Kagome lattice is stable at low temperatures and low pressure, but that it transforms into a hexagonal lattice with alternating attractive and repulsive bands on increasing pressure.

cond-mat.soft↗

arXiv2010

Cluster theory of Janus particles

We apply a simple statistical mechanics cluster approximation for studying clustering in the Kern and Frenkel model of Janus fluids. The approach is motivated by recent Monte Carlo simulations work on the same model revealing that the vapor coexisting with the liquid phase contains clusters of different sizes and shapes whose equilibrium concentrations in general depend on the interaction range as well as on thermodynamic parameters. The approximation hinges on a separation between the intra- and inter-cluster contribution to thermodynamics, where only the former is explicitly computed by Monte Carlo simulations. Two levels of a simple liquid theory approximation are exploited for the description of the latter. In the first we use the ideal-gas expressions and obtain a qualitative agreement with extensive Monte Carlo bulk simulations. This can be improved to a semi-quantitative agreement, by using a hard-sphere description for the cluster-cluster correlations.

cond-mat.soft↗

arXiv2010

From caging to Rouse dynamics in polymer melts with intramolecular barriers: a critical test of the Mode Coupling Theory

By means of computer simulations and solution of the equations of the Mode Coupling Theory (MCT), we investigate the role of the intramolecular barriers on several dynamic aspects of non-entangled polymers. The investigated dynamic range extends from the caging regime characteristic of glass-formers to the relaxation of the chain Rouse modes. We review our recent work on this question, provide new results and critically discuss the limitations of the theory. Solutions of the MCT for the structural relaxation reproduce qualitative trends of simulations for weak and moderate barriers. However a progressive discrepancy is revealed as the limit of stiff chains is approached. This disagreement does not seem related with dynamic heterogeneities, which indeed are not enhanced by increasing barrier strength. It is not connected either with the breakdown of the convolution approximation for three-point static correlations, which retains its validity for stiff chains. These findings suggest the need of an improvement of the MCT equations for polymer melts. Concerning the relaxation of the chain degrees of freedom, MCT provides a microscopic basis for time scales from chain reorientation down to the caging regime. It rationalizes, from first principles, the observed devations from the Rouse model on increasing the barrier strength. These include anomalous scaling of relaxation times, long-time plateaux, and non-monotonous wavelength dependence of the mode correlators.

cond-mat.soft↗

arXiv2010

A numerical study of one-patch colloidal particles: from square-well to Janus

We perform numerical simulations of a simple model of one-patch colloidal particles to investigate: (i) the behavior of the gas-liquid phase diagram on moving from a spherical attractive potential to a Janus potential and (ii) the collective structure of a system of Janus particles. We show that, for the case where one of the two hemispheres is attractive and one is repulsive, the system organizes into a dispersion of orientational ordered micelles and vesicles and, at low $T$, the system can be approximated as a fluid of such clusters, interacting essentially via excluded volume. The stability of this cluster phase generates a very peculiar shape of the gas and liquid coexisting densities, with a gas coexistence density which increases on cooling, approaching the liquid coexistence density at very low $T$.

cond-mat.soft↗

arXiv2010

Theoretical description of a DNA-linked nanoparticle self-assembly

Nanoparticles tethered with DNA strands are promising building blocks for bottom-up nanotechnology, and a theoretical understanding is important for future development. Here we build on approaches developed in polymer physics to provide theoretical descriptions for the equilibrium clustering and dynamics, as well as the self-assembly kinetics of DNA-linked nanoparticles. Striking agreement is observed between the theory and molecular modeling of DNA tethered nanoparticles.

cond-mat.soft↗

arXiv2010

Effects of patch size and number within a simple model of patchy colloids

We report on a computer simulation and integral equation study of a simple model of patchy spheres, each of whose surfaces is decorated with two opposite attractive caps, as a function of the fraction $χ$ of covered attractive surface. The simple model explored --- the two-patch Kern-Frenkel model --- interpolates between a square-well and a hard-sphere potential on changing the coverage $χ$. We show that integral equation theory provides quantitative predictions in the entire explored region of temperatures and densities from the square-well limit $χ= 1.0$ down to $χ\approx 0.6$. For smaller $χ$, good numerical convergence of the equations is achieved only at temperatures larger than the gas-liquid critical point, where however integral equation theory provides a complete description of the angular dependence. These results are contrasted with those for the one-patch case. We investigate the remaining region of coverage via numerical simulation and show how the gas-liquid critical point moves to smaller densities and temperatures on decreasing $χ$. Below $χ\approx 0.3$, crystallization prevents the possibility of observing the evolution of the line of critical points, providing the angular analog of the disappearance of the liquid as an equilibrium phase on decreasing the range for spherical potentials. Finally, we show that the stable ordered phase evolves on decreasing $χ$ from a three-dimensional crystal of interconnected planes to a two-dimensional independent-planes structure to a one-dimensional fluid of chains when the one-bond-per-patch limit is eventually reached.

cond-mat.soft↗

arXiv2009

Phase diagram of Janus Particles

We deeply investigate a simple model representative of the recently synthesized Janus particles, i.e. colloidal spherical particles whose surface is divided into two areas of different chemical composition. When the two surfaces are solvophilic and solvophobic, these particles constitute the simplest example of surfactants. The phase diagram includes a colloidal-poor (gas) colloidal-rich (liquid) de-mixing region, which is progressively suppressed by the insurgence of micelles, providing the first model where micellization and phase-separation are simultaneously observed. The coexistence curve is found to be negatively sloped in the temperature-pressure plane, suggesting that Janus particles can provide a colloidal system with anomalous thermodynamic behavior.

cond-mat.soft↗

arXiv2009

Disconnected Glass-Glass Transitions and Diffusion Anomalies in a Model with two Repulsive Length Scales

Building on mode-coupling-theory calculations, we report a novel scenario for multiple glass transitions in a purely repulsive spherical potential: the square-shoulder. The liquid-glass transition lines exhibit both melting by cooling and melting by compression as well as associated diffusion anomalies, similar to the ones observed in water. Differently from all previously investigated models, here for small shoulder widths a glass-glass line is found that is disconnected from the liquid phase. Upon increasing the shoulder width such a glass-glass line merges with the liquid-glass transition lines, featuring two distinct endpoint singularities that give rise to logarithmic decays in the dynamics. These findings can be explained analytically by the interplay of different repulsive length scales.

cond-mat.stat-mech↗

arXiv2009

Phase diagram and structural properties of a simple model for one-patch particles

We study the thermodynamic and structural properties of a simple, one-patch fluid model using the reference hypernetted-chain (RHNC) integral equation and specialized Monte Carlo simulations. In this model, the interacting particles are hard spheres, each of which carries a single identical, arbitrarily-oriented, attractive circular patch on its surface; two spheres attract via a simple square-well potential only if the two patches on the spheres face each other within a specific angular range dictated by the size of the patch. For a ratio of attractive to repulsive surface of 0.8, we construct the RHNC fluid-fluid separation curve and compare with that obtained by Gibbs ensemble and grand canonical Monte Carlo simulations. We find that RHNC provides a quick and highly reliable estimate for the position of the fluid-fluid critical line. In addition, it gives a detailed (though approximate) description of all structural properties and their dependence on patch size.

cond-mat.soft↗

arXiv2009

Colloidal systems with competing interactions: from an arrested repulsive cluster phase to a gel

We report an extensive numerical study of a charged colloidal system with competing short-range depletion attraction and long-range electrostatic repulsion. By analizing the cluster properties, we identify two distinct regions in the phase diagram: a state composed of stable finite-size clusters, whose relative interactions are dominated by long-range repulsion, and a percolating network. Both states are found to dynamically arrest at low temperatures, providing evidence of the existence of two distinct non-ergodic states in these systems: a Wigner glass of clusters and a gel.

cond-mat.soft↗