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.

Simplified self-consistent theory of colloid dynamics.

One of the main elements of the self-consistent generalized Langevin equation (SCGLE) theory of colloid dynamics [Phys. Rev. E 62, 3382 (2000); 72, 031107 (2005)] is the introduction of exact short-time moment conditions in its formulation. The need to previously calculate these exact short-time properties constitutes a practical barrier for its application. In this Brief Report, we report that a simplified version of this theory, in which this short-time information is eliminated, leads to the same results in the intermediate and long-time regimes. Deviations are only observed at short times, and are not qualitatively or quantitatively important. This is illustrated by comparing the two versions of the theory for representative model systems.

Self-consistent generalized Langevin equation for colloid dynamics.

We present a general self-consistent theory of colloid dynamics which, for a system without hydrodynamic interactions, allows us to calculate F(k,t), and its self-diffusion counterpart F(S)(k,t), given the effective interaction pair potential u(r) between colloidal particles, and the corresponding equilibrium static structural properties. This theory is build upon the exact results for F(k,t) and F(S)(k,t) in terms of a hierarchy of memory functions, derived from the application of the generalized Langevin equation formalism, plus the proposal of Vineyard-like connections between F(k,t) and F(S)(k,t) through their respective memory functions, and a closure relation between these memory functions and the time-dependent friction function Delta zeta(t). As an illustrative application, we present and analyze a selection of numerical results of this theory in the short- and intermediate-time regimes, as applied to a two-dimensional repulsive Yukawa Brownian fluid. For this system, we find that our theory accurately describes the dynamic properties contained in F(k,t) in a wide range of conditions, including strongly correlated systems, at the longest times available from our computer simulations.

Overdamped van hove function of colloidal suspensions

The generalized-hydrodynamic theory for collective diffusion of a monodisperse colloidal suspension is developed in the framework of the Onsager-Machlup theory of time-dependent fluctuations. The time evolution of the intermediate scattering function F(k,t) is derived as a contraction of the description involving the instantaneous particle number concentration, the particle current, and the stress tensor of the Brownian fluid as state variables. We show that the proper overdamped limit of this equation requires the explicit separation of the stress tensor in its mutually orthogonal kinetic and configurational contributions. Analogous results also follow for the self-intermediate scattering function F(s)(k,t). We show that neglecting the non-Markovian part of the configurational stress tensor memory, one recovers the single exponential memory approximation (based on sum rules derived from the Smoluchowski equation) for both F(s)(k,t) and F(k,t). We suggest simple approximate manners to relate the collective and the self-memory functions, leading to Vineyard-like approximate relations between F(s)(k,t) and F(k,t).

Vineyard-like approximations for colloid dynamics

In this paper we propose a hierarchy of higher-order Vineyard-like approximations for colloidal systems. These consist of approximate expressions for the intermediate scattering function F(k,t) in terms of the self-intermediate scattering function F(s)(k,t) (or some memory function associated with it), and of other static structural properties of the suspension. In order to assess the accuracy of the proposed approximations, we perform Brownian dynamics simulations in a simple model system (a two-dimensional Yukawa Brownian fluid), in which we determine F(k,t), F(s)(k,t), and the required static structural properties. We study proposals for "second-order" and "third-order" Vineyard-like approximations. We find that the detailed structure of the relationship between the corresponding collective and self-memory functions turns out to be most important, as quantified by our simulation results.