We study the Brownian motion of a charged colloid, confined between two charged walls, for small separation between the colloid and the walls. The system is embedded in an ionic solution. The combined effect of electrostatic repulsion and reduced diffusion due to hydrodynamic forces results in a specific motion in the direction perpendicular to the confining walls. The apparent diffusion coefficient at short times as well as the diffusion characteristic time are shown to follow a sigmoid curve as function of a dimensionless parameter. This parameter depends on the electrostatic properties and can be controlled by tuning the solution ionic strength. At low ionic strength, the colloid moves faster and is localized, while at high ionic strength it moves slower and explores a wider region between the walls, resulting in a larger diffusion characteristic time.
Within the framework of a Modified Poisson-Boltzmann theory accounting for steric effects of microions, we prove analytically that the effective pair interactions between like-charge colloids immersed in a confined electrolyte are repulsive. Our approach encompasses and extends previously known results to the case of complete confinement, and further incorporates the finite size of the microions which is absent in the standard Poisson-Boltzmann theory.
In a recent study [Phys. Rev. E 60, 6530 (1999)], Trizac and Raimbault showed that the effective pair interaction between like charged colloids immersed in a cylindrically confined electrolyte remains repulsive even when the size of the micro-ions or the finite longitudinal extension of the confining cylinder are taken into account. Contrary to their claim, we argue that the case of finite longitudinal confinement doesn't always generate repulsive interactions and to illustrate this point we also provide a simple example.
The effective interaction between charged colloidal particles confined between two planar like-charged walls is investigated using computer simulations of the primitive model describing asymmetric electrolytes. In detail, we calculate the effective force acting onto a single macroion and onto a macroion pair in the presence of slit-like confinement. For moderate Coulomb coupling, we find that this force is repulsive. Under strong coupling conditions, however, the sign of the force depends on the distance to the plates and on the interparticle distance. In particular, the particle-plate interac…
Colloids held by optical or magnetic tweezers have been used to explore the local rheological properties of a complex medium and to extract work from fluctuations with some appropriate protocols. However, a general theoretical understanding of the interplay between the confinement and the interaction with the environment is still lacking. Here, we explore the statistical properties of the position of a probe confined in a harmonic trap moving at constant velocity and interacting with a bath of colloidal particles maintained at a different temperature. Interactions among particles are accounted…
The analytical expressions for the time-dependent cross-correlations of the translational and rotational Brownian displacements of a particle with arbitrary shape are derived. The reference center is arbitrary, and the reference frame is such that the rotational-rotational diffusion tensor is diagonal.
The deviatoric stresses of colloidal suspensions are routinely calculated using the expression introduced by Batchelor [J. Fluid Mech. 83, 97--117 (1977)]. We show by example that the central feature in its derivation, the thermodynamic force driving particles down the density gradient, is inconsistent with the motion of the colloids. A new expression for the stress is proposed.
We consider the sedimentation of a colloidal gel under confinement in the direction of gravity. The confinement allows us to compare directly experiments and computer simulations, for the same system size in the vertical direction. The confinement also leads to qualitatively different behaviour compared to bulk systems: in large systems gelation suppresses sedimentation, but for small systems sedimentation is enhanced relative to non-gelling suspensions, although the rate of sedimentation is reduced when the strength of the attraction between the colloids is strong. We map interaction paramete…
Using molecular dynamics simulations we study the slow dynamics of a hard sphere fluid confined in a disordered porous matrix. The presence of both discontinuous and continuous glass transitions as well as the complex interplay between single-particle and collective dynamics are well captured by a recent extension of mode-coupling theory for fluids in porous media. The degree of universality of the mode-coupling theory predictions for related models of colloids is studied by introducing size-disparity between fluid and matrix particles, as well as softness in the interactions.
Brownian motion of colloidal particles in the quasi-two-dimensional (qTD) confinement displays distinct kinetic characters from that in bulk. Here we experimentally report a dynamic evolution of Brownian particles in the qTD system. The dynamic system displays a quasi-equilibrium state of colloidal particles performing Brownian motion. In the quasi-equilibrium process, the qTD confinement results in the coupling of particle motions, which slowly dampens the motion and interaction of particles until the final equilibrium state reaches. The theory is developed to explain coupling motions of Brow…
We theoretically investigate general properties of driven (sheared) colloidal suspensions in confinement, based on methods of classical density functional theory. In the absence of an exact closed (Smoluchowski-) equation for the one-particle density under shear, we formulate a set of general conditions for approximations, and show that a simple closure fulfills them. The exact microscopic stress tensor is identified. Exemplifying the situation near a wall (oriented parallel to the direction of shear), we note that the microscopic shear stress is not necessarily homogeneous. Formulating a seco…
In his Comment (cond-mat/0104060) to [Phys. Rev. E 60, 6530 (1999)], Mateescu shows that while the effective interactions remain repulsive when the specific size of the micro-ions is taken into account via a Modified Poisson-Boltzmann equation, a similar conclusion cannot be reached for the situation of complete lateral confinement. This point is correct but has already been considered in a more general study [Phys. Rev. E 62, R1465 (2000), where repulsion is generically obtained]; moreover, we argue that it illustrates the irrelevancy of the notion of pair potential in completely confined con…
We synthesize colloidal particles with various anisotropic shapes and track their orientationally resolved Brownian trajectories using confocal microscopy. An analysis of appropriate short-time correlation functions provides direct access to the hydrodynamic friction tensor of the particles revealing nontrivial couplings between the translational and rotational degrees of freedom. The results are consistent with calculations of the hydrodynamic friction tensor in the low-Reynolds-number regime for the experimentally determined particle shapes.
We study a colloidal suspension confined between two quasi-parallel walls as a model system for glass transitions in confined geometries. The suspension is a mixture of two particle sizes to prevent wall-induced crystallization. We use confocal microscopy to directly observe the motion of colloidal particles. This motion is slower in confinement, thus producing glassy behavior in a sample which is a liquid in an unconfined geometry. For higher volume fraction samples (closer to the glass transition), the onset of confinement effects occurs at larger length scales.
The traction on the surface of a spherical active colloid in a thermally fluctuating Stokesian fluid contains passive, active, and Brownian contributions. Here we derive these three parts systematically, by "projecting out" the fluid using the boundary-domain integral representation of slow viscous flow. We find an exact relation between the statistics of the Brownian traction and the thermal forces in the fluid and derive, thereby, fluctuation-dissipation relations for every irreducible tensorial harmonic traction mode. The first two modes give the Brownian force and torque, from which we con…
We study the non-equilibrium coarsening dynamics of a binary liquid solvent around a colloidal particle in a presence of a time-dependent temperature gradient that emerges after temperature quench of a suitably coated colloid surface. The solvent is maintained at its critical concentration and the colloid is fixed in space. The coarsening patterns near the surface are shown to be strongly dependent on the colloid surface adsorption properties and on the temperature evolution. The temperature gradient alters the morphology of a binary solvent near the surface of a colloid as compared to the coa…
We review recent progress in the theoretical description of anisotropic hard colloidal particles. The shapes considered range from rods and dumbbells to rounded cubes, polyhedra and to biaxial particles with arbitrary shape. Our focus is on both static and dynamical density functional theory and on computer simulations. We describe recent results for the structure, dynamics and phase behaviour in the bulk and in various confining geometries, e.g. established by two parallel walls which reduce the dimensionality of the system to two dimensions. We also include recent theoretical modelling for a…
We investigate the Brownian motion of boomerang colloidal particles confined between two glass plates. Our experimental observations show that the mean displacements are biased towards the center of hydrodynamic stress (CoH), and that the mean-square displacements exhibit a crossover from short time faster to long time slower diffusion with the short-time diffusion coefficients dependent on the points used for tracking. A model based on Langevin theory elucidates that these behaviors are ascribed to a superposition of two diffusive modes: the ellipsoidal motion of the CoH and the rotational mo…
Understanding the relationship between colloidal building block shape and self-assembled material structure is important for the development of novel materials by self-assembly. In this regard, colloidal superballs are unique building blocks because their shape can smoothly transition between spherical and cubic. Assembly of colloidal superballs under spherical confinement results in macroscopic clusters with ordered internal structure. By utilizing Small Angle X-Ray Scattering (SAXS), we probe the internal structure of colloidal superball dispersion droplets during confinement. We observe and…
We present a simple chemical strategy for the formation of a self-propelling cluster via the process of capture and assembly of passive colloids on the surface of a chemically active colloid. The two species of colloids that are isotropic and Brownian otherwise interact to form propelling cluster. With the help of coarse-grained numerical simulations, we show that a chemically active colloid can induce diffusiophoretic motility to nearby chemically inert colloids towards itself. This propulsion and then self-assembly can then lead to the formation of active cluster. We observe the formation of…
Hypothesis: The collective dynamics and self-assembly of colloids floating at a fluid/fluid interface is a balance between deterministic lateral interaction forces, viscous resistance to colloid motion along the surface and thermal (Brownian) fluctuations. As the colloid size decreases, thermal forces become important and can affect the self assembly into ordered patterns and crystal structures that are the starting point for various materials applications. Numerics: Langevin dynamic simulations involving two particles straddling a liquid/liquid interface with a high viscosity contrast are pre…
The friction and diffusion coefficients of rigid spherical colloidal particles dissolved in a fluid are determined from velocity and force autocorrelation functions by mesoscale hydrodynamic simulations. Colloids with both slip and no-slip boundary conditions are considered, which are embedded in fluids modelled by multiparticle collision dynamics (MPC) with and without angular momentum conservation. For no-slip boundary conditions, hydrodynamics yields the well-known Stokes law, while for slip boundary conditions the lack of angular momentum conservation leads to a reduction of the hydrodynam…
As recently reported [Turiv T. et al., Science, 2013, Vol. 342, 1351], fluctuations in the orientation of the liquid crystal (LC) director can transfer momentum from the LC to a colloid, such that the diffusion of the colloid becomes anomalous on a short time scale. Using video microscopy and single particle tracking, we investigate random thermal motion of colloidal particles in a nematic liquid crystal for the time scales shorter than the expected time of director fluctuations. At long times, compared to the characteristic time of the nematic director relaxation we observe typical anisotropi…
We study the Brownian motion of particles trapped by optical tweezers inside a colloidal glass (Laponite) during the sol-gel transition. We use two methods based on passive rheology to extract the effective temperature from the fluctuations of the Brownian particles. All of them give a temperature that, within experimental errors, is equal to the heat bath temperature. Several interesting features concerning the statistical properties and the long time correlations of the particles are observed during the transition.
We describe a method to simulate the dynamics of charged colloidal particles suspended in a liquid containing dissociated ions and salt ions. Regimes of prime current interest are those of large volume fraction of colloids, highly charged particles and low salt concentrations. A description which is tractable under these conditions is obtained by treating the small dissociated and salt ions as continuous fields, while keeping the colloidal macroions as discrete particles. For each spatial configuration of the macroions, the electrostatic potential arising from all charges in the system is dete…
In the simplest realization of Brownian motion, a colloidal sphere moves randomly in an isotropic fluid; its mean squared displacement (MSD) grows linearly with time $\textitτ$. Brownian motion in an orientationally ordered fluid, a nematic, is anisotropic, with the MSD being larger along the axis of molecular orientation, called the director. We show that at short time scales, the anisotropic diffusion in a nematic becomes also anomalous, with the MSD growing slower (subdiffusion) and faster (superdiffusion) than $\textitτ$. The anomalous diffusion occurs at time scales that correspond to the…
We study a dense colloidal suspension confined between two quasiparallel glass plates as a model system for a supercooled liquid in confined geometries. We directly observe the three-dimensional Brownian motion of the colloidal particles using laser scanning confocal microscopy. The particles form dense layers along the walls, but crystallization is avoided as we use a mixture of two particle sizes. A normally liquid-like sample, when confined, exhibits slower diffusive motion. Particle rearrangements are spatially heterogeneous, and the shapes of the rearranging regions are strongly influence…
The non-thermal nature of self-propelling colloids offers new insights into non-equilibrium physics. The central mathematical model to describe their trajectories is active Brownian motion, where a particle moves with a constant speed, while randomly changing direction due to rotational diffusion. While several feedback strategies exist to achieve position-dependent velocity, the possibility of spatial and temporal control over rotational diffusion, which is inherently dictated by thermal fluctuations, remains untapped. Here, we decouple rotational diffusion from thermal noise. Using external …
Designing and fabricating self-assembled open colloidal crystals have become one major direction in soft matter community because of many promising applications associated with open colloidal crystals. However, most of the self-assembled crystals found in experiments are not open but close-packed. Here by using computer simulation, we systematically investigate the self-assembly of oppositely charged colloidal hard spheres confined between two parallel hard walls, and we find that the confinement can stabilize multi-layer NaCl-like (simple cubic) open crystals. The maximal layers of stable NaC…
Long-range hydrodynamics between colloidal particles or fibers is modelled by the Fluid Particle Model. Two methods are considered to impose the fluid boundary conditions at colloidal surfaces. In the first method radial and transverse friction forces between particle and solvent are applied such that the correct friction and torque follows for moving or rotating particles. The force coefficients are calculated analytically and checked by numerical simulation. In the second method a collision rule is used between colloidal particle and solvent particle that imposes the stick boundary condition…
In a system of colloidal inclusions suspended in a thermalized bath of smaller particles, the bath engenders an attractive force between the inclusions, arising mainly from entropic origins, known as the depletion force. In the case of active bath particles, the nature of the bath-mediated force changes dramatically from an attractive to a repulsive one, as the strength of particle activity is increased. We study such bath-mediated effective interactions between colloidal inclusions in a bath of self-propelled Brownian particles, being confined in a narrow planar channel. Confinement is found …
Theory and simulation of Brownian colloids suspended in an implicit solvent, with the hydrodynamics of the fluid accounted for by effective interactions between the colloids, are shown to yield a marked and hitherto unobserved discrepancy between the viscosity calculated from the average shear stress under an imposed shear rate in the Stokesian regime and the viscosity extracted by the Green-Kubo formalism from the auto-correlations of thermal stress fluctuations in quiescent equilibrium. We show that agreement between both methods is recovered by accounting for the fluctuating Brownian stress…
We study the effective electrostatic interactions between a pair of charged colloidal particles without salt ions while the system is confined in two dimensions. In particular we use a simplified model to elucidate the effects of rotational fluctuations in counterion distribution. The results exhibit effective colloidal attractions under appropriate conditions. Meanwhile, long-range repulsions persist over most of our studied cases. The repulsive forces arise from the fact that in two dimensions the charged colloids cannot be perfectly screened by counterions, as the residual quadrupole moment…
Ring, or cyclic, polymers have unique properties compared to linear polymers, due to their topologically closed structure that has no beginning or end. Experimental measurements on molecular ring polymers are challenging due to their polydispersity in molecular weight and the presence of undesired side products such as chains. Here, we study an experimental model system for cyclic polymers, that consists of rings of flexibly-linked micron-sized colloids with $n$=4..8 segments. We characterize the conformations of these flexible colloidal rings and find that they are freely-jointed up to steric…
The individual motion of a colloidal particle is described by an overdamped Langevin equation. When rotational degrees of freedom are relevant, these are described by a corresponding Langevin process. Our purpose is to show that the microscopic local density of colloids, in terms of a space and rotation state, also evolves according to a Langevin equation. The latter can then be used as the starting point of a variety of approaches, ranging from dynamical density functional theory to mode-coupling approximations.
We study the phase behavior of hard spheres confined between two parallel hard plates using extensive computer simulations. We determine the full equilibrium phase diagram for arbitrary densities and plate separations from one to five hard-sphere diameters using free energy calculations. We find a first-order fluid-solid transition, which corresponds to either capillary freezing or melting depending on the plate separation. The coexisting solid phase consists of crystalline layers with either triangular or square symmetry. Increasing the plate separation, we find a sequence of crystal structur…
We investigate the average velocity of Brownian particles driven by a constant external force when constrained to move in two-dimensional, weakly-corrugated channels. We consider both the geometric confinement of the particles between solid walls as well as the soft confinement induced by a periodic potential. Using perturbation methods we show that the leading order correction to the marginal probability distribution of particles in the case of soft confinement is equal to that obtained in the case of geometric confinement, provided that the (configuration) integral over the cross-section of …
The aggregation of interacting Brownian particles in sheared concentrated suspensions is an important issue in colloid and soft matter science per se. Also, it serves as a model to understand biochemical reactions occurring in vivo where both crowding and shear play an important role. We present an effective medium approach within the Smoluchowski equation with shear which allows one to calculate the encounter kinetics through a potential barrier under shear at arbitrary colloid concentrations. Experiments on a model colloidal system in simple shear flow support the validity of the model in th…
Under partial confinement, the motion of colloidal particles is restricted to a plane but their dynamics is influenced by hydrodynamic interactions mediated by the unconfined, three--dimensional flow of the embedding fluid. We demonstrate that this dimensionality mismatch induces a characteristic divergence in the two--dimensional collective diffusion coefficient of the colloidal monolayer. This result, independent from the specific interparticle forces in the monolayer, is solely due to the kinematical constraint on the colloidal particles, and it is different from the known divergence of tra…
The influence of hydrodynamic interactions on lane formation of oppositely charged driven colloidal suspensions is investigated using Brownian dynamics computer simulations performed on the Rotne-Prager level of the mobility tensor. Two cases are considered, namely sedimentation and electrophoresis. In the latter case the Oseen contribution to the mobility tensor is screened due to the opposite motion of counterions. The simulation results are compared to that resulting from simple Brownian dynamics where hydrodynamic interactions are neglected. For sedimentation, we find that hydrodynamic int…
Shape changes resulting from segmental flexibility are ubiquitous in molecular and biological systems, and are expected to affect both the diffusive motion and (biological) function of dispersed objects. The recent development of colloidal structures with freely-jointed bonds have now made a direct experimental investigation of diffusive shape-changing objects possible. Here, we show the effect of segmental flexibility on the simplest possible model system, a freely-jointed cluster of three spherical particles, and validate long-standing theoretical predictions. We find that in addition to the…
We present a model of anomalous diffusion consisting of an ensemble of particles undergoing homogeneous Brownian motion except for confinement by randomly placed reflecting boundaries. For power-law distributed compartment sizes, we calculate exact and asymptotic values of the ensemble averaged mean squared displacement and find that it increases subdiffusively, as either a power or the logarithm of time. Numerical simulations show that the probability density function of the displacement is non-Gaussian. We discuss the relevance of the model for the analysis of single-particle tracking experi…
We use computer simulations to test a simple idea for mapping between long-time self diffusivities obtained from molecular and Brownian dynamics. The strategy we explore is motivated by the behavior of fluids comprising particles that interact via inverse-power-law pair potentials, which serve as good reference models for dense atomic or colloidal materials. Based on our simulation data, we present an empirical expression that semi-quantitatively describes the "atomic" to "colloidal" diffusivity mapping for inverse-power-law fluids, but also for model complex fluids with considerably softer (s…
We describe in detail how to implement a coarse-grained hybrid Molecular Dynamics and Stochastic Rotation Dynamics simulation technique that captures the combined effects of Brownian and hydrodynamic forces in colloidal suspensions. The importance of carefully tuning the simulation parameters to correctly resolve the multiple time and length-scales of this problem is emphasized. We systematically analyze how our coarse-graining scheme resolves dimensionless hydrodynamic numbers such as the Reynolds number, the Schmidt number, the Mach number, the Knudsen number, and the Peclet number. The many…
Colloidal gel aging is investigated using very long runs of brownian dynamics simulations. The Asakura Oosawa description of the depletion interaction is used to model a simple colloid polymer mixture. Several regimes are identified during gel formation. The Intermediate scattering function displays a double decay characteristic of systems where some kinetic processes are frozen. The $β$ relaxation at short times is explained in terms of the Krall-Weitz model for the decorelation due to the elastic modes present. The $α$ relaxation at long times is well described by a stretched exponential, sh…
We develop a formally exact technique for obtaining steady-state distributions of non-interacting active Brownian particles in a variety of systems. Our technique draws on results from the theory of two-way diffusion equations to solve the steady-state Smoluchowski equation for the 1-particle distribution function. The methods are employed to study in detail three scenarios: 1) confinement in a channel, 2) a constant flux steady state, and 3) sedimentation in a uniform external field. In each scenario, known behaviors are reproduced and precisely quantified, and new results are presented. In p…
We apply a hybrid Molecular Dynamics and mesoscopic simulation technique to study the steady-state sedimentation of hard sphere particles for Peclet numbers (Pe) ranging from 0.08 to 12. Hydrodynamic back-flow causes a reduction of the average sedimentation velocity relative to the Stokes velocity. We find that this effect is independent of Pe number. Velocity fluctuations show the expected effects of thermal fluctuations at short correlation times. At longer times, non-equilibrium hydrodynamic fluctuations are visible, and their character appears to be independent of the thermal fluctuations.…
The exact analytical expressions for the time-dependent cross-correlations of the translational and rotational Brownian displacements of a particle with arbitrary shape were derived by us in [J. Chem. Phys. 142, 214902 (2015) and 144, 076101 (2016)]. They are in this work applied to construct a method to analyze Brownian motion of a particle of an arbitrary shape, and to extract accurately the self-diffusion matrix from the measurements of the cross-correlations, which in turn allows to gain some information on the particle structure. As an example, we apply our new method to analyze the exper…
This paper presents experimental results about transport of dilute suspensions of nano-objects in silicon-glass micrometric and sub-micrometric channels. Two kinds of objects are used: solid, rigid latex beads and spherical capsule-shaped, soft polymersomes. They are tracked using fluorescence microscopy. Three parameters are studied: confinement (ratio between particle diameter and channel depth), Brownian diffusion and particle nature. The aim of this work is to understand how these different parameters affect the transport of suspensions in narrow channels and to understand the different me…
Miniaturized, self-propelled locomotors use chemo-mechanical transduction mechanisms to convert fuel in the environment to autonomous motion. Recent experimental and theoretical studies demonstrate that these autonomous engines can passively follow the contours of solid boundaries they encounter. Boundary guidance, however, is not necessarily stable: Mechanical disturbances can cause the motor to hydrodynamically depart from the passively guided pathway. Furthermore, given the scaled-down size of micromotors (typically 100 nm -10 $μ$m), Brownian thermal fluctuation forces are necessarily impor…
Using grand canonical Monte Carlo simulations, we investigate the percolation behavior of a square well fluid with an ultra-short range of attraction in three dimension (3D) and in confined geometry. The latter is defined through two parallel and structureless walls (slit-pore). We focus on temperatures above the critical temperature of the (metastable) condensation transition of the 3D system. Investigating a broad range of systems sizes, we first determine the percolation thresholds, i. e., the critical packing fraction for percolation $η_{c}$. For the slit-pore systems, $η_{c}$ is found to …
