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Register a new userMany-body critical Casimir interactions in colloidal suspensions
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We study the fluctuation-induced Casimir interactions in colloidal suspensions, especially between colloids immersed in a binary liquid close to its critical demixing point. To simulate these systems, we present a highly efficient cluster Monte Carlo algorithm based on geometric symmetries of the Hamiltonian. Utilizing the principle of universality, the medium is represented by an Ising system while the colloids are areas of spins with fixed orientation. Our results for the Casimir interaction potential between two particles at the critical point in two dimensions perfectly agree with the exact predictions. However, we find that in finite systems the behavior strongly depends on whether the $Z_{2}$ symmetry of the system is broken by the particles. Eventually we present Monte Carlo results for the three-body Casimir interaction potential and take a close look onto the case of one particle in the vicinity of two adjacent particles, which can be calculated from the two-particle interaction by a conformal mapping. These results emphasize the failure of the common decomposition approach for many-particle critical Casimir interactions.
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A recent Letter [Phys. Rev. Lett. 103, 156101 (2009)] reports the experimental observation of aggregation of colloidal particles dispersed in a liquid mixture of heavy water and 3-methylpyridine. The experimental data are interpreted in terms of a model which accounts solely for the competing effects of the interparticle electrostatic repulsion and of the attractive critical Casimir force. Here we show, however, that the reported aggregation actually occurs within ranges of values of the correlation length and of the Debye screening length ruled out by the proposed model and that a significant part of the experimental data presented in the Letter cannot be consistently interpreted in terms of such a model.
We study the collective dynamics of colloidal suspensions in the presence of a time-dependent potential, by means of dynamical density functional theory. We consider a non-linear diffusion equation for the density and show that spatial patterns emerge from a sinusoidal external potential with a time-dependent wavelength. These patterns are characterized by a sinusoidal density with the average wavelength and a Bessel-function envelope with an induced wavelength that depends only on the amplitude of the temporal oscillations. As a generalization of this result, we propose a design strategy to obtain a family of spatial patterns using time-dependent potentials of practically arbitrary shape.
If a fluctuating medium is confined, the ensuing perturbation of its fluctuation spectrum generates Casimir-like effective forces acting on its confining surfaces. Near a continuous phase transition of such a medium the corresponding order parameter fluctuations occur on all length scales and therefore close to the critical point this effect acquires a universal character, i.e., to a large extent it is independent of the microscopic details of the actual system. Accordingly it can be calculated theoretically by studying suitable representative model systems. We report on the direct measurement of critical Casimir forces by total internal reflection microscopy (TIRM), with femto-Newton resolution. The corresponding potentials are determined for individual colloidal particles floating above a substrate under the action of the critical thermal noise in the solvent medium, constituted by a binary liquid mixture of water and 2,6-lutidine near its lower consolute point. Depending on the relative adsorption preferences of the colloid and substrate surfaces with respect to the two components of the binary liquid mixture, we observe that, upon approaching the critical point of the solvent, attractive or repulsive forces emerge and supersede those prevailing away from it. Based on the knowledge of the critical Casimir forces acting in film geometries within the Ising universality class and with equal or opposing boundary conditions, we provide the corresponding theoretical predictions for the sphere-planar wall geometry of the experiment. The experimental data for the effective potential can be interpreted consistently in terms of these predictions and a remarkable quantitative agreement is observed.
We investigate critical phenomena in colloids by means of the renormalization-group based hierarchical reference theory of fluids (HRT). We focus on three experimentally relevant model systems: namely, the Asakura-Oosawa model of a colloidal dispersion under the influence of polymer-induced attractive depletion forces; fluids with competing short-range attractive and longer-range repulsive interactions; solutions of star-polymers whose pair potential presents both an attractive well and an ultrasoft repulsion at shorter distance. Our results show that the ability to tune the effective interactions between colloidal particles allows one to generate a variety of crossovers to the asymptotic critical behavior, which are not observed in atomic fluids.
Based on primitive model computer simulations with explicit microions, we calculate the effective interactions in a binary mixture of charged colloids with species $A$ and $B$ for different size and charge ratios. An optimal pairwise interaction is obtained by fitting the many-body effective forces. This interaction is close to a Yukawa (or Derjaguin-Landau-Verwey-Overbeek(DLVO)) pair potential but the $AB$ cross-interaction is different from the geometric mean of the two direct $AA$ and $BB$ interactions. As a function of charge asymmetry, the corresponding nonadditivity parameter is first positive, then getting significantly negative and is getting then positive again. We finally show that an inclusion of nonadditivity within an optimal effective Yukawa model gives better predictions for the fluid pair structure than DLVO-theory.
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