Condensed Matter Theory

Abstract:

The conventional assumption that the self-diffusion coefficient of a small tracer can be obtained by a local and instantaneous application of Einstein's relation in a temperature field with spatial and temporal heterogeneity is revisited. It is shown that hydrodynamic fluctuations contribute to the self-diffusion tensor in a universal way, i.e. independent of the size and shape of the tracer. The hydrodynamic contribution is anisotropic--it reflects knowledge of the global anisotropy in the temperature profile, leading to anisotropic self-diffusion tensor for a spherical tracer. It is also retarded--it creates memory effects during the diffusion process due to hydrodynamic interactions.

Abstract:

Computer simulations and theory are used to systematically investigate how the effective force between two big colloidal spheres in a sea of small spheres depends on the basic (big-small and small-small) interactions. The latter are modeled as hardcore pair potentials with a Yukawa tail which can be either repulsive or attractive. For a repulsive small-small interaction, the effective force follows the trends as predicted by a mapping onto an effective nonadditive hardcore mixture: both a depletion attraction and an accumulation repulsion caused by small spheres adsorbing onto the big ones can be obtained depending on the sign of the big-small interaction. For repulsive big-small interactions, the effect of adding a small-small attraction also follows the trends predicted by the mapping. But a more subtle "repulsion through attraction" effect arises when both big-small and small-small attractions occur: upon increasing the strength of the small-small interaction, the effective potential becomes more repulsive. We have further tested several theoretical methods against our computer simulations: The superposition approximation works best for an added big-small repulsion, and breaks down for a strong big-small attraction, while density functional theory is very accurate for any big-small interaction when the small particles are pure hard spheres. The theoretical methods perform most poorly for small-small attractions.