Theory of orientational ordering in colloidal molecular crystals

Freezing of charged colloids on square or triangular two-dimensional periodic substrates has been recently shown to realize a rich variety of orientational orders. We propose a theoretical framework to analyze the corresponding structures. A fundamental ingredient is that a non spherical charged object in an electrolyte creates a screened electrostatic potential that is anisotropic at any distance. Our approach is in excellent agreement with the known experimental and numerical results, and explains in simple terms the reentrant orientational melting observed in these so called colloidal molecular crystals. We also investigate the case of a rectangular periodic substrate and predict an unusual phase transition between orientationnaly ordered states, as the aspect ratio of the unit cell is changed.Comment: 4 pages, to appear in Phys. Rev. Let

Active Brownian Motion Tunable by Light

Active Brownian particles are capable of taking up energy from their environment and converting it into directed motion; examples range from chemotactic cells and bacteria to artificial micro-swimmers. We have recently demonstrated that Janus particles, i.e. gold-capped colloidal spheres, suspended in a critical binary liquid mixture perform active Brownian motion when illuminated by light. In this article, we investigate in some more details their swimming mechanism leading to active Brownian motion. We show that the illumination-borne heating induces a local asymmetric demixing of the binary mixture generating a spatial chemical concentration gradient, which is responsible for the particle's self-diffusiophoretic motion. We study this effect as a function of the functionalization of the gold cap, the particle size and the illumination intensity: the functionalization determines what component of the binary mixture is preferentially adsorbed at the cap and the swimming direction (towards or away from the cap); the particle size determines the rotational diffusion and, therefore, the random reorientation of the particle; and the intensity tunes the strength of the heating and, therefore, of the motion. Finally, we harness this dependence of the swimming strength on the illumination intensity to investigate the behaviour of a micro-swimmer in a spatial light gradient, where its swimming properties are space-dependent

Trapping colloids near chemical stripes via critical Casimir forces

We study theoretically and experimentally the solvent-mediated critical Casimir force acting on colloidal particles immersed in a binary liquid mixture of water and 2,6-lutidine and close to substrates which are chemically patterned with periodically alternating stripes of antagonistic adsorption preferences. These patterns are experimentally realized via microcontact printing. Upon approaching the critical demixing point of the solvent, normal and lateral critical Casimir forces generate laterally confining effective potentials for the colloids. We analyze in detail the rich behavior of the spherical colloids close to such substrates. For all patterned substrates we investigated, our measurements of these effective potentials agree with the corresponding theoretical predictions. Since both the directions and the strengths of the critical Casimir forces can be tuned by minute temperature changes, this provides a new mechanism for controlling colloids as model systems, opening encouraging perspectives for applications.Comment: Invited contribution to Molecular Physics Special Issue on Bob Evans' 65th birthda

Understanding depletion forces beyond entropy

The effective interaction energy of a colloidal sphere in a suspension containing small amounts of non-ionic polymers and a flat glass surface has been measured and calculated using total internal reflection microscopy (TIRM) and a novel approach within density functional theory (DFT), respectively. Quantitative agreement between experiment and theory demonstrates that the resulting repulsive part of the depletion forces cannot be interpreted entirely in terms of entropic arguments but that particularly at small distances ($\lesssim$ 100 nm) attractive dispersion forces have to be taken into account

Phase Transitions of Soft Disks in External Periodic Potentials: A Monte Carlo Study

The nature of freezing and melting transitions for a system of model colloids interacting by a DLVO potential in a spatially periodic external potential is studied using extensive Monte Carlo simulations. Detailed finite size scaling analyses of various thermodynamic quantities like the order parameter, its cumulants etc. are used to map the phase diagram of the system for various values of the reduced screening length $\kappa a_{s}$ and the amplitude of the external potential. We find clear indication of a reentrant liquid phase over a significant region of the parameter space. Our simulations therefore show that the system of soft disks behaves in a fashion similar to charge stabilized colloids which are known to undergo an initial freezing, followed by a re-melting transition as the amplitude of the imposed, modulating field produced by crossed laser beams is steadily increased. Detailed analysis of our data shows several features consistent with a recent dislocation unbinding theory of laser induced melting

Frustration and Melting of Colloidal Molecular Crystals

Using numerical simulations we show that a variety of novel colloidal crystalline states and multi-step melting phenomena occur on square and triangular two-dimensional periodic substrates. At half-integer fillings different kinds of frustration effects can be realized. A two-step melting transition can occur in which individual colloidal molecules initially rotate, destroying the overall orientational order, followed by the onset of interwell colloidal hopping, in good agreement with recent experiments.Comment: 6 pages, 3 postscript figures. Procedings of International Conference on Strongly Coupled Coulomb Systems, Santa Fe, 200

Phase Transitions of Hard Disks in External Periodic Potentials: A Monte Carlo Study

The nature of freezing and melting transitions for a system of hard disks in a spatially periodic external potential is studied using extensive Monte Carlo simulations. Detailed finite size scaling analysis of various thermodynamic quantities like the order parameter, its cumulants etc. are used to map the phase diagram of the system for various values of the density and the amplitude of the external potential. We find clear indication of a re-entrant liquid phase over a significant region of the parameter space. Our simulations therefore show that the system of hard disks behaves in a fashion similar to charge stabilized colloids which are known to undergo an initial freezing, followed by a re-melting transition as the amplitude of the imposed, modulating field produced by crossed laser beams is steadily increased. Detailed analysis of our data shows several features consistent with a recent dislocation unbinding theory of laser induced melting.Comment: 36 pages, 16 figure

Critical Casimir effect in classical binary liquid mixtures

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.Comment: 30 pages, 17 figure

Archimedean-like colloidal tilings on substrates with decagonal and tetradecagonal symmetry

Two-dimensional colloidal suspensions subject to laser interference patterns with decagonal symmetry can form an Archimedean-like tiling phase where rows of squares and triangles order aperiodically along one direction [J. Mikhael et al., Nature 454, 501 (2008)]. In experiments as well as in Monte-Carlo and Brownian dynamics simulations, we identify a similar phase when the laser field possesses tetradecagonal symmetry. We characterize the structure of both Archimedean-like tilings in detail and point out how the tilings differ from each other. Furthermore, we also estimate specific particle densities where the Archimedean-like tiling phases occur. Finally, using Brownian dynamics simulations we demonstrate how phasonic distortions of the decagonal laser field influence the Archimedean-like tiling. In particular, the domain size of the tiling can be enlarged by phasonic drifts and constant gradients in the phasonic displacement. We demonstrate that the latter occurs when the interfering laser beams are not adjusted properly

On the nature of long-range contributions to pair interactions between charged colloids in two dimensions

We perform a detailed analysis of solutions of the inverse problem applied to experimentally measured two-dimensional radial distribution functions for highly charged latex dispersions. The experiments are carried out at high colloidal densities and under low-salt conditions. At the highest studied densities, the extracted effective pair potentials contain long-range attractive part. At the same time, we find that for the best distribution functions available the range of stability of the solutions is limited by the nearest neighbour distance between the colloidal particles. Moreover, the measured pair distribution functions can be explained by purely repulsive pair potentials contained in the stable part of the solution.Comment: 6 pages, 5 figure