Dynamics of a suspension of interacting yolk-shell particles

In this work we study the self-diffusion properties of a liquid of hollow spherical particles (shells)bearing a smaller solid sphere in their interior (yolks). We model this system using purely repulsive hard-body interactions between all (shell and yolk) particles, but assume the presence of a background ideal solvent such that all the particles execute free Brownian motion between collisions,characterized by short-time self-diffusion coefficients D0s for the shells and D0y for the yolks. Using a softened version of these interparticle potentials we perform Brownian dynamics simulations to determine the mean squared displacement and intermediate scattering function of the yolk-shell complex. These results can be understood in terms of a set of effective Langevin equations for the N interacting shell particles, pre-averaged over the yolks' degrees of freedom, from which an approximate self-consistent description of the simulated self-diffusion properties can be derived. Here we compare the theoretical and simulated results between them, and with the results for the same system in the absence of yolks. We find that the yolks, which have no effect on the shell-shell static structure, influence the dynamic properties in a predictable manner, fully captured by the theory.Comment: 5 pages, 1 figur

From equilibrium to non-equilibrium statistical mechanics of liquids

Relevant and fundamental concepts of the statistical mechanical theory of classical liquids are ordinarily introduced in the context of the description of thermodynamic equilibrium states. This makes explicit reference to probability distribution functions of \emph{equilibrium} statistical ensembles (canonical, microcanonical, ...) in the derivation of general and fundamental relations between inter-particle interactions and measurable macroscopic properties of a given system. This includes, for instance, expressing the internal energy and the pressure as functionals of the radial distribution function, or writing transport coefficients (diffusion constant, linear viscosity, ...) in terms of integral relations involving both, static and dynamic auto-correlation functions (density-density, stress-stress, ...). Most commonly, however, matter is not in thermodynamic equilibrium, and this calls for the extension of these relations to out-of-equilibrium conditions with the aim of understanding, for example, the time-dependent transient states during the process of equilibration, or the aging of glass- and gel-forming liquids during the formation of non-equilibrium amorphous solid states. In this work we address this issue from both, a general perspective and an illustrative concrete application focused on the first principles description of rheological and viscoelastic properties of glass- and gel-forming liquids

Rescaled mean spherical approximation for colloidal mixtures

In this work, the rescaled mean spherical approximation (RMSA) for colloidal mixtures interacting via a DLVO-type potential is developed, and its application to suspensions of highly charged macroions is illustrated. For this purpose we introduce a simple scheme to solve the mean spherical approximation (MSA) for Yukawa mixtures with factorized coupling parameters. This scheme consists of the mapping of the Yukawa system onto a corresponding primitive model system. Such a correspondence is used as a device for the calculation of the static structure functions of the original Yukawa mixture. Within this scheme, a straightforward implementation of the rescaling procedure is performed, which allows for the calculation of partial structure factors in strongly interacting mixtures. The rescaling procedure we use is an extension of that introduced by Hansen and Hayter for monodisperse suspensions. The structure factors obtained with the rescaled mean spherical approximation compare well with computer simulation results. The advantages and limitations of the RMSA are also discussed in some detail.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/28352/1/0000113.pd

Density Fluctuations in an Electrolyte from Generalized Debye-Hueckel Theory

Near-critical thermodynamics in the hard-sphere (1,1) electrolyte is well described, at a classical level, by Debye-Hueckel (DH) theory with (+,-) ion pairing and dipolar-pair-ionic-fluid coupling. But DH-based theories do not address density fluctuations. Here density correlations are obtained by functional differentiation of DH theory generalized to {\it non}-uniform densities of various species. The correlation length $\xi$ diverges universally at low density $\rho$ as $(T\rho)^{-1/4}$ (correcting GMSA theory). When $\rho=\rho_c$ one has $\xi\approx\xi_0^+/t^{1/2}$ as $t\equiv(T-T_c)/T_c\to 0+$ where the amplitudes $\xi_0^+$ compare informatively with experimental data.Comment: 5 pages, REVTeX, 1 ps figure included with epsf. Minor changes, references added. Accepted for publication in Phys. Rev. Let

Dynamic equivalence between atomic and colloidal liquids

We show that the kinetic-theoretical self-diffusion coefficient of an atomic fluid plays the same role as the short-time self-diffusion coefficient D_S in a colloidal liquid, in the sense that the dynamic properties of the former, at times much longer than the mean free time, and properly scaled with D_S, will indistinguishable from those of a colloidal liquid with the same interaction potential. One important consequence of such dynamic equivalence is that the ratio D_L/ D_S of the long-time to the short-time self-diffusion coefficients must then be the same for both, an atomic and a colloidal system characterized by the same inter-particle interactions. This naturally extends to atomic fluids a well-known dynamic criterion for freezing of colloidal liquids[Phys. Rev. Lett. 70, 1557 (1993)]. We corroborate these predictions by comparing molecular and Brownian dynamics simulations on (soft- and hard-sphere) model systems, representative of what we may refer to as the "hard-sphere" dynamic universality class

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 {\bf 62}, 3382 (2000); ibid {\bf 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 note 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.Comment: 1 text archive, 3 figure