Depletion potential in hard-sphere mixtures: theory and applications

We determine the depletion-induced phase-behavior of hard sphere colloids and interacting polymers by large-scale Monte Carlo simulations using very accurate coarse-graining techniques. A comparison with standard Asakura-Oosawa model theories and simulations shows that including excluded volume interactions between polymers leads to qualitative differences in the phase diagrams. These effects become increasingly important for larger relative polymer size. Our simulations resu...

We analyze the structure of the Fundamental Measure Theory for the free energy density functional of hard sphere mixtures. A comparative study of the different versions of the theory, and other density functional approaches, is done in terms of their generic form for the three-points direct correlation function, which shows clearly the main advantages and problems of the different approximations. A recently developed version for the monocomponent case is extended to mixtures ...

We study the depletion interaction between spherical particles of radius R immersed in a dilute solution of rigid rods of length L. The computed interaction potential is, within numerical accuracy, exact for any value of L/R. In particular we find that for L of order R, the depth of the depletion well is smaller than the prediction of the Derjaguin approximation. Our results bring new light into the discussion on the lack of phase separation in colloidal mixtures of spheres a...

Given the ubiquity of depletion effects in biological and other soft matter systems, it is desirable to have coarse-grained Molecular Dynamics simulation approaches appropriate for the study of complex systems. This paper examines the use of two common truncated Lennard-Jones (WCA) potentials to describe a pair of colloidal particles in a thermal bath of depletants. The shifted-WCA model is the steeper of the two repulsive potentials considered, while the combinatorial-WCA mo...

Explicit simulations of fluid mixtures of highly size-dispersed particles are constrained by numerical challenges associated with identifying pair-interaction neighbors. Recent algorithmic developments have ameliorated these difficulties to an extent, permitting more efficient simulations of systems with many large and small particles of disperse sizes. We leverage these capabilities to perform molecular dynamics simulations of binary sphere mixtures with elastically stiff pa...

Hard spheres are a central and important model reference system for both homogeneous and inhomogeneous fluid systems. In this paper we present new high-precision molecular-dynamics computer simulations for a hard sphere fluid at a planar hard wall. For this system we present benchmark data for the density profile $\rho(z)$ at various bulk densities, the wall surface free energy $\gamma$, the excess adsorption $\Gamma$, and the excess volume $v_{ex}$, which is closely related ...

Using a simple density functional theory (DFT) we determine the height of the free energy barrier for forming a droplet of the liquid phase from the metastable gas phase for a model colloidal fluid exhibiting competing interactions. The pair potential has a hard core of diameter {\sigma}, is attractive Yukawa at intermediate separations, and is repulsive Yukawa at large separations. We find that even a very weak long-range repulsive tail in the pair potential has a profound e...

We introduce a general physical formulation that allows one to obtain uniquely the effectiveinteractions by contracting the bare forces, even in highly concentrated systems. We tested it bystudying depletion forces in two-dimensional binary and ternary colloidal mixtures with a totalpacking fraction up to 70%. Our result opens up the possibility of finding an efficient route todetermine effective interactions at finite concentration and even at thermodynamic conditions nearto...

The possibility to induce demixing in a colloidal mixture by adding small polymers, or other equivalent depletant agents, is theoretically investigated. By use of Mean Field Theory, suitably generalized to deal with short range effective interactions, the phase diagram of a binary mixture ofcolloidal particles (modelled as hard spheres) in a solvent is determined as a function of the polymer concentration on the basis of the Asakura-Oosawa model.The topology of the phase diag...

We investigate effective interactions between a colloidal particle, immersed in a binary mixture of smaller spheres, and a semipermeable membrane. The colloid is modeled as a big hard sphere and the membrane is represented as an infinitely thin surface which is fully permeable to one of the smaller spheres and impermeable to the other one. Within the framework of the density functional theory we evaluate the depletion potentials, and we consider two different approximate theo...