Nearly-logarithmic decay in the colloidal hard-sphere system

Nearly-logarithmic decay is identified in the data for the mean-squared displacement of the colloidal hard-sphere system at the liquid-glass transition [v. Megen et. al, Phys. Rev. E 58, 6073(1998)]. The solutions of mode-coupling theory for the microscopic equations of motion fit the experimental data well. Based on these equations, the nearly-logarithmic decay is explained as the equivalent of a beta-peak phenomenon, a manifestation of the critical relaxation when the coupling between of the probe variable and the density fluctuations is strong. In an asymptotic expansion, a Cole-Cole formula including corrections is derived from the microscopic equations of motion, which describes the experimental data for three decades in time.Comment: 4 pages, 3 figure

Relaxation in a glassy binary mixture: Mode-coupling-like power laws, dynamic heterogeneity and a new non-Gaussian parameter

We examine the relaxation of the Kob-Andersen Lennard-Jones binary mixture using Brownian dynamics computer simulations. We find that in accordance with mode-coupling theory the self-diffusion coefficient and the relaxation time show power-law dependence on temperature. However, different mode-coupling temperatures and power laws can be obtained from the simulation data depending on the range of temperatures chosen for the power-law fits. The temperature that is commonly reported as this system's mode-coupling transition temperature, in addition to being obtained from a power law fit, is a crossover temperature at which there is a change in the dynamics from the high temperature homogeneous, diffusive relaxation to a heterogeneous, hopping-like motion. The hopping-like motion is evident in the probability distributions of the logarithm of single-particle displacements: approaching the commonly reported mode-coupling temperature these distributions start exhibiting two peaks. Notably, the temperature at which the hopping-like motion appears for the smaller particles is slightly higher than that at which the hopping-like motion appears for the larger ones. We define and calculate a new non-Gaussian parameter whose maximum occurs approximately at the time at which the two peaks in the probability distribution of the logarithm of displacements are most evident.Comment: Submitted for publication in Phys. Rev.

Mode-Coupling Theory as a Mean-Field Description of the Glass Transition

Mode-coupling theory (MCT) is conjectured to be a mean-field description of dynamics of the structural glass transition and the replica theory to be its thermodynamic counterpart. However, the relationship between the two theories remains controversial and quantitative comparison is lacking. In this Letter, we investigate MCT for monatomic hard sphere fluids at arbitrary dimensions above three and compare the results with replica theory. We find grave discrepancies between the predictions of two theories. While MCT describes the nonergodic parameter quantitatively better than the replica theory in three dimension, it predicts a completely different dimension dependence of the dynamical transition point. We find it to be due to the pathological behavior of the nonergodic parameters derived from MCT, which exhibit negative tails in real space at high dimensions.Comment: 5 pages, to appear in Phys. Rev. Lett.: Typos have been correcte

A critical test of the mode-coupling theory of the glass transition

The mode-coupling theory of the glass transition predicts the time evolution of the intermediate scattering functions in viscous liquids on the sole basis of the structural information encoded in two-point density correlations. We provide a critical test of this property and show that the theory fails to describe the qualitatively distinct dynamical behavior obtained in two model liquids characterized by very similar pair correlation functions. Because we use `exact' static information provided by numerical simulations, our results are a direct proof that some important information about the dynamics of viscous liquids is not captured by pair correlations, and is thus not described by the mode-coupling theory, even in the temperature regime where the theory is usually applied.Comment: 7 pages, 5 figures

Multi-scale coarse-graining of diblock copolymer self-assembly: from monomers to ordered micelles

Starting from a microscopic lattice model, we investigate clustering, micellization and micelle ordering in semi-dilute solutions of AB diblock copolymers in a selective solvent. To bridge the gap in length scales, from monomers to ordered micellar structures, we implement a two-step coarse graining strategy, whereby the AB copolymers are mapped onto ``ultrasoft'' dumbells with monomer-averaged effective interactions between the centres of mass of the blocks. Monte Carlo simulations of this coarse-grained model yield clear-cut evidence for self-assembly into micelles with a mean aggregation number n of roughly 100 beyond a critical concentration. At a slightly higher concentration the micelles spontaneously undergo a disorder-order transition to a cubic phase. We determine the effective potential between these micelles from first principles.Comment: 4 pages, 4 figures, submitted to Phys. Rev. Lett

Connections of activated hopping processes with the breakdown of the Stokes-Einstein relation and with aspects of dynamical heterogeneities

We develop a new extended version of the mode-coupling theory (MCT) for glass transition, which incorporates activated hopping processes via the dynamical theory originally formulated to describe diffusion-jump processes in crystals. The dynamical-theory approach adapted here to glass-forming liquids treats hopping as arising from vibrational fluctuations in quasi-arrested state where particles are trapped inside their cages, and the hopping rate is formulated in terms of the Debye-Waller factors characterizing the structure of the quasi-arrested state. The resulting expression for the hopping rate takes an activated form, and the barrier height for the hopping is ``self-generated'' in the sense that it is present only in those states where the dynamics exhibits a well defined plateau. It is discussed how such a hopping rate can be incorporated into MCT so that the sharp nonergodic transition predicted by the idealized version of the theory is replaced by a rapid but smooth crossover. We then show that the developed theory accounts for the breakdown of the Stokes-Einstein relation observed in a variety of fragile glass formers. It is also demonstrated that characteristic features of dynamical heterogeneities revealed by recent computer simulations are reproduced by the theory. More specifically, a substantial increase of the non-Gaussian parameter, double-peak structure in the probability distribution of particle displacements, and the presence of a growing dynamic length scale are predicted by the extended MCT developed here, which the idealized version of the theory failed to reproduce. These results of the theory are demonstrated for a model of the Lennard-Jones system, and are compared with related computer-simulation results and experimental data.Comment: 13 pages, 5 figure

Fluids confined in wedges and by edges: Virial series for the line-thermodynamic properties of hard spheres

This work is devoted to analyze the relation between the thermodynamic properties of a confined fluid and the shape of its confining vessel. Recently, new insights in this topic were found through the study of cluster integrals for inhomogeneous fluids that revealed the dependence on the vessel shape of the low density behavior of the system. Here, the statistical mechanics and thermodynamics of fluids confined in wedges or by edges is revisited, focusing on their cluster integrals. In particular, the well known hard sphere fluid, which was not studied in this framework so far, is analyzed under confinement and its thermodynamic properties are analytically studied up to order two in the density. Furthermore, the analysis is extended to the confinement produced by a corrugated wall. These results rely on the obtained analytic expression for the second cluster integral of the confined hard sphere system as a function of the opening dihedral angle 0 < β < 2π. It enables a unified approach to both wedges and edges.Fil: Urrutia, Ignacio. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Slow Dynamics of the High Density Gaussian Core Model

We numerically study crystal nucleation and glassy slow dynamics of the one-component Gaussian core model (GCM) at high densities. The nucleation rate at a fixed supersaturation is found to decrease as the density increases. At very high densities, the nucleation is not observed at all in the time window accessed by long molecular dynamics (MD) simulation. Concomitantly, the system exhibits typical slow dynamics of the supercooled fluids near the glass transition point. We compare the simulation results of the supercooled GCM with the predictions of mode-coupling theory (MCT) and find that the agreement between them is better than any other model glassformers studied numerically in the past. Furthermore, we find that a violation of the Stokes-Einstein relation is weaker and the non-Gaussian parameter is smaller than canonical glassformers. Analysis of the probability distribution of the particle displacement clearly reveals that the hopping effect is strongly suppressed in the high density GCM. We conclude from these observations that the GCM is more amenable to the mean-field picture of the glass transition than other models. This is attributed to the long-ranged nature of the interaction potential of the GCM in the high density regime. Finally, the intermediate scattering function at small wavevectors is found to decay much faster than its self part, indicating that dynamics of the large-scale density fluctuations decouples with the shorter-ranged caging motion.Comment: 15 pages, 13 figure

Spatial correlations in sheared isothermal liquids : From elastic particles to granular particles

Spatial correlations for sheared isothermal elastic liquids and granular liquids are theoretically investigated. Using the generalized fluctuating hydrodynamics, correlation functions for both the microscopic scale and the macroscopic scale are obtained. The existence of the long-range correlation functions obeying power laws has been confirmed. The validity of our theoretical predictions have been verified from the molecular dynamics simulation.Comment: 34 pages, 12 figure

Experimental Comparisons of Derivative Free Optimization Algorithms

In this paper, the performances of the quasi-Newton BFGS algorithm, the NEWUOA derivative free optimizer, the Covariance Matrix Adaptation Evolution Strategy (CMA-ES), the Differential Evolution (DE) algorithm and Particle Swarm Optimizers (PSO) are compared experimentally on benchmark functions reflecting important challenges encountered in real-world optimization problems. Dependence of the performances in the conditioning of the problem and rotational invariance of the algorithms are in particular investigated.Comment: 8th International Symposium on Experimental Algorithms, Dortmund : Germany (2009