Structural relaxation, dynamical arrest, and aging in soft-sphere liquids.

We investigate the structural relaxation of a soft-sphere liquid quenched isochorically (ϕ = 0.7) and instantaneously to different temperatures Tf above and below the glass transition. For this, we combine extensive Brownian dynamics simulations and theoretical calculations based on the non-equilibrium self-consistent generalized Langevin equation (NE-SCGLE) theory. The response of the liquid to a quench generally consists of a sub-linear increase of the α-relaxation time with system's age. Approaching the ideal glass-transition temperature from above (Tf > Ta), sub-aging appears as a transient process describing a broad equilibration crossover for quenches to nearly arrested states. This allows us to empirically determine an equilibration timescale teq(Tf) that becomes increasingly longer as Tf approaches Ta. For quenches inside the glass (Tf ≤ Ta), the growth rate of the structural relaxation time becomes progressively larger as Tf decreases and, unlike the equilibration scenario, τα remains evolving within the whole observation time-window. These features are consistently found in theory and simulations with remarkable semi-quantitative agreement and coincide with those revealed in a previous and complementary study [P. Mendoza-Méndez et al., Phys. Rev. 96, 022608 (2017)] that considered a sequence of quenches with fixed final temperature Tf = 0 but increasing ϕ toward the hard-sphere dynamical arrest volume fraction ϕHS a=0.582. The NE-SCGLE analysis, however, unveils various fundamental aspects of the glass transition, involving the abrupt passage from the ordinary equilibration scenario to the persistent aging effects that are characteristic of glass-forming liquids. The theory also explains that, within the time window of any experimental observation, this can only be observed as a continuous crossover.

Dynamic arrest within the self-consistent generalized Langevin equation of colloid dynamics.

This paper presents a recently developed theory of colloid dynamics as an alternative approach to the description of phenomena of dynamic arrest in monodisperse colloidal systems. Such theory, referred to as the self-consistent generalized Langevin equation (SCGLE) theory, was devised to describe the tracer and collective diffusion properties of colloidal dispersions in the short- and intermediate-time regimes. Its self-consistent character, however, introduces a nonlinear dynamic feedback, leading to the prediction of dynamic arrest in these systems, similar to that exhibited by the well-established mode coupling theory of the ideal glass transition. The full numerical solution of this self-consistent theory provides in principle a route to the location of the fluid-glass transition in the space of macroscopic parameters of the system, given the interparticle forces (i.e., a nonequilibrium analog of the statistical-thermodynamic prediction of an equilibrium phase diagram). In this paper we focus on the derivation from the same self-consistent theory of the more straightforward route to the location of the fluid-glass transition boundary, consisting of the equation for the nonergodic parameters, whose nonzero values are the signature of the glass state. This allows us to decide if a system, at given macroscopic conditions, is in an ergodic or in a dynamically arrested state, given the microscopic interactions, which enter only through the static structure factor. We present a selection of results that illustrate the concrete application of our theory to model colloidal systems. This involves the comparison of the predictions of our theory with available experimental data for the nonergodic parameters of model dispersions with hard-sphere and with screened Coulomb interactions.

Structure of polyelectrolyte complexes by Brownian dynamics simulation: effects of the bond length asymmetry of the polyelectrolytes.

Brownian dynamics simulations were performed to study the structure of polyelectrolyte complexes formed by two flexible, oppositely charged polyelectrolyte chains. The distribution of monomers in the complex as well as the radius of gyration and structure factor of complexes and individual polyelectrolytes are reported. These structural properties were calculated for polyelectrolyte chains with equal number of monomers, keeping constant the bond length of the negative chain and increasing the bond length of the positive chain. This introduces an asymmetry in the length of the chains that modulates the final structure of the complexes. In the symmetric case the distribution of positive and negative monomers in the complex are identical, producing clusters that are locally and globally neutral. Deviations from the symmetric case lead to nonuniform, asymmetric monomer distributions, producing net charge oscillations inside the complex and large changes in the radius of gyration of the complex and individual chains. From the radius of gyration of the polyelectrolyte chains it is shown that the positive chain is much more folded than the negative chain when the chains are asymmetric, which is also confirmed through the scaling behavior of the structure factors.

State diagram for the electrostatic adsorption of charged colloids on confining walls: simulation and theory.

We study the structure of charged colloidal suspensions under confinement and determine a state diagram for the occurrence of electrostatic adsorption onto the confining walls, an effect that results in the accumulation of particles on the bounding surfaces and that could be relevant in experiments. We use Monte Carlo simulations to quantify this structural transition and perform theoretical calculations based on integral equations. Overall, our results provide a guide for experimentalists dealing with charged colloidal systems to determine the relevance of this purely electrostatic effect.

Axial and angular correlations between colloidal particles in narrow cylindrical pores

In this work we present a study of the local structure of a model colloidal suspension highly confined inside a cylindrical pore. Such a study is based in Monte Carlo computer simulations, using the repulsive part of the Derjaguin-Landau-Verwey-Overbeek potential as the pair interaction between particles. The structural properties calculated here are the concentration profile n(rho), the axial pair correlation function g(z), and the axial-angular pair correlation function g(z,straight phi). The behavior of these quantities is analyzed as a function of the density of colloidal particles in the restricted space, and as a function of the size of the pore.