Fluctuations of the interface between coexisting colloidal fluid phases have been measured with confocal microscopy. Due to a very low surface tension, the thermal motions of the interface are so slow, that a record can be made of the positions of the interface. The theory of the interfacial height fluctuations is developed. For a host of correlation functions, the experimental data are compared with the theoretical expressions. The agreement between theory and experiment is remarkably good.
Colloidal particles are not simple rigid particles, in general an isolated particle is a system with many degrees of freedom in its own right, e.g., the counterions around a charged colloidal particle.The behaviour of model colloidal particles, with a simple phenomenological model to account for these degrees of freedom, is studied. It is found that the interaction between the particles is not pairwise additive. It is even possible that the interaction between a triplet of particles is attractive while the pair interaction is repulsive. When this is so the liquid phase is either stable only in…
Surface effects are generally prevailing in confined colloidal systems. Here we report on dispersed nanoparticles close to a fluid membrane. Exact results regarding the static organization are derived for a dilute solution of non-adhesive colloids. It is shown that thermal fluctuations of the membrane broaden the density profile, but on average colloids are neither accumulated nor depleted near the surface. The radial correlation function is also evaluated, from which we obtain the effective pair-potential between colloids. This entropically-driven interaction shares many similarities with the…
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…
From microscopic fluid clusters to macroscopic droplets, the structure of fluids is governed by the Van der Waals force, a force that acts between polarizable objects. In this Letter, we derive a general theory that describes the non-equilibrium counterpart to the Van der Waals force, which emerges in spatially coherently fluctuating electromagnetic fields. We describe the formation of a novel and complex hierarchy of self-organized morphologies in magnetic and dielectric colloid systems. Most striking among these morphologies are dipolar foams - colloidal superstructures that swell against gr…
The resolution of Brownian motion in simulations of micro-particle suspensions can be crucial to reproducing the correct dynamics of individual particles, as well as providing an accurate characterisation of suspension properties. Including these effects in simulations, however, can be computationally intensive due to the configuration dependent random displacements that would need to be determined at every time step. In this paper, we introduce the fluctuating force-coupling method (FCM) to overcome this difficulty, providing a fast approach to simulate colloidal suspensions at large-scale. W…
We discuss the stochastic thermodynamics of systems that are described by a time-dependent density field, for example simple liquids and colloidal suspensions. For a time-dependent change of external parameters, we show that the Jarzynski relation connecting work with the change of free energy holds if the time evolution of the density follows the Kawasaki-Dean equation. Specifically, we study the work distributions for the compression and expansion of a two-dimensional colloidal model suspension implementing a practical coarse-graining scheme of the microscopic particle positions. We demonstr…
We combine experiments and theory to investigate the dynamics and orientational fluctuations of ferromagnetic microellipsoids that form a ribbon-like structure due to attractive dipolar forces. When assembled in the ribbon, the ellipsoids displays orientational thermal uctuations with an amplitude that can be controlled via application of an in-plane magnetic field. We use video microscopy to investigate the orientational dynamics in real time/space. Theoretical arguments are used to derive an analytical expression that describes how the distribution of the different angular configurations dep…
The lattice Boltzmann algorithm efficiently simulates the Navier Stokes equation of isothermal fluid flow, but ignores thermal fluctuations of the fluid, important in mesoscopic flows. We show how to adapt the algorithm to include noise, satisfying a fluctuation-dissipation theorem (FDT) directly at lattice level: this gives correct fluctuations for mass and momentum densities, and for stresses, at all wavevectors $k$. Unlike previous work, which recovers FDT only as $k\to 0$, our algorithm offers full statistical mechanical consistency in mesoscale simulations of, e.g., fluctuating colloidal …
Using a refractive index matching method, we investigate the trajectories of particles in a three dimensional granular packing submitted to cyclic shear deformation. The particle motion observed during compaction is not diffusive but exhibits transient cage effect, similar to the one observed in colloidal glasses. We precisely study the statistics of the step size between two successive cycles and observe that it is proportional to the shear amplitude. The link between the microscopic observations and the macroscopic evolution of the volume fraction during compaction is discussed.
The effects of confinement on colloidal self-assembly in the case of fixed number of confined particles are studied in the one dimensional lattice model solved exactly in the Grand Canonical Ensemble (GCE) in [J. Pękalski et al. J. Chem. Phys. 142, 014903 (2015)]. The model considers a pair interaction defined by a short-range attraction plus a longer-range repulsion. We consider thermodynamic states corresponding to self-assembly into clusters. Both, fixed and adaptive boundaries are studied. For fixed boundaries, there are particular states in which, for equal average densities, the number o…
Studies by video microscopy on fluctuating colloids measure the real-space cross-correlations in particle motion. This set of correlations is then treated as a matrix, in order to study the spectrum and mode structure. We show that in general the modes are modified by the truncation of the full real-space correlations. We perform a theoretical analysis of the truncation, find the boundary conditions imposed by the truncation, and propose practical windowing strategies to eliminate artefacts. We study the problem from various perspectives, to compile a survey for experimentalists.
We present a new method based on the scattering technique to investigate fluctuation-induced forces at a fluid interface. The scattering approach, well suited to the study of many body systems of arbitrary geometries, is augmented to include boundary fluctuations. Using this method, we study the deviation of the total fluctuation-induced interaction from the sum of pairwise energies for three colloidal particles. We consider both frozen and fluctuating colloids and obtain a very good agreement between analytical and numerical results. We find a marked difference in the three body fluctuation-i…
We describe and implement a technique for extracting forces from the relaxation of an overdamped thermal system with normal modes. At sufficiently short time intervals, the evolution of a normal mode is well described by a one-dimensional Smoluchowski equation with constant drift velocity, v, and diffusion coefficient, D. By virtue of fluctuation-dissipation, these transport coefficients are simply related to conservative forces, F, acting on the normal mode: F = k_BT v/D. This relationship implicitly accounts for hydrodynamic interactions, requires no mechanical calibration, makes no assumpti…
We examine the effects of thermal fluctuations on thin elastic filaments with non-circular cross-section and arbitrary spontaneous curvature and torsion. Analytical expressions for orientational correlation functions and for the persistence length of helices are derived, and it is found that this length varies non-monotonically with the strength of thermal fluctuations. In the weak fluctuation regime, the local helical structure is preserved and the statistical properties are dominated by long wavelength bending and torsion modes. As the amplitude of fluctuations is increased, the helix ``melt…
We consider an ensemble of spherical colloidal particles immersed in a near-critical solvent such as a binary liquid mixture close to its critical demixing point. The emerging long-ranged fluctuations of the corresponding order parameter of the solvent drive the divergence of the correlation length. Spatial confinements of these critical fluctuations by colloidal solute particles, acting as cavities in the fluctuating medium, restrict and modify the fluctuation spectrum in a way which depends on their relative configuration. This results in effective, so-called critical Casimir forces (CCFs) a…
Colloidal systems offer unique opportunities for the study of phase formation and structure since their characteristic length scales are accessible to visible light. As a model system the two dimensional assembly of colloidal magnetic and non-magnetic particles dispersed in a ferrofluid (FF) matrix is studied by transmission optical microscopy. We present a method to statistically evaluate images with thousands of particles and map phases by extraction of local variables. Different lattice structures and long-range connected branching chains are observed, when tuning the effective magnetic int…
In a dense colloidal suspension at a volume fraction slightly lower than that of its glass transition, we follow the trajectories of an assembly of tracers over a large time window. We define a local activity, which quantifies the local tendency of the system to rearrange. We determine the statistics of the time and space integrated activity, and we argue that it develops a low activity tail that comes on a par with the onset of glassy behavior and heterogeneous dynamics. These rare events may be interpreted as the reflection of an underlying dynamic phase transition.
We perform Brownian dynamics simulations of semiflexible colloidal sheets with hydrodynamic interactions and thermal fluctuations in shear flow. As a function of the ratio of bending rigidity to shear energy (a dimensionless quantity we denote $S$) and the ratio of bending rigidity to thermal energy, we observe a dynamical transition from stochastic flipping to crumpling and continuous tumbling. This dynamical transition is broadened by thermal fluctuations, and the value of $S$ at which it occurs is consistent with the onset of chaotic dynamics found for athermal sheets. The effects of differ…
Studying the jamming transition of granular and colloidal systems, has lead to a proliferation of theoretical and numerical results formulated in the language of the eigenspectrum of the dynamical matrix for these disordered system. Only recently however, these modes have been accessed experimentally in colloidal and granular media, computing the eigenmodes of the covariance matrix of the particle positions. At the same time new conceptual and methodological questions have appeared, regarding the interpretation of these results. In the present paper, we first give an overview of the theoretica…
In this paper, we view fluctuating fronts made of particles on a one-dimensional lattice as an extreme value problem. The idea is to denote the configuration for a single front realization at time $t$ by the set of co-ordinates $\{k_i(t)\}\equiv[k_1(t),k_2(t),...,k_{N(t)}(t)]$ of the constituent particles, where $N(t)$ is the total number of particles in that realization at time $t$. When $\{k_i(t)\}$ are arranged in the ascending order of magnitudes, the instantaneous front position can be denoted by the location of the rightmost particle, i.e., by the extremal value $k_f(t)=\text{max}[k_1(t)…
Coarse-graining atomic displacements in a solid produces both local affine strains and "non-affine" fluctuations. Here we study the equilibrium dynamics of these coarse grained quantities to obtain space-time dependent correlation functions. We show how a subset of these thermally excited, non-affine fluctuations act as precursors for the nucleation of lattice defects and suggest how defect probabilities may be altered by an {\it experimentally realisable} "external" field conjugate to the global non-affinity parameter. Our results are amenable to verification in experiments on colloidal cryst…
We develop the scattering formalism to calculate the interaction between colloidal particles trapped at a fluid interface. Since, in addition to the interface, the colloids may also fluctuate in this system, we implement the fluctuation of the boundaries into the scattering formalism and investigate how the interaction between colloids is modified by their fluctuations. This general method can be applied to any number of colloids with various geometries at an interface. We apply the formalism derived in this work to a system of spherical colloids at the interface between two fluid phases. For …
Anomalous statistics in the Langevin equation with fluctuating diffusivity: from Brownian yet non-Gaussian diffusion to anomalous diffusion and ergodicity breaking
Tokyo University of Science（东京科学大学）；Pohang University of Science and Technology（浦项科技大学）；Asia Pacific Centre for Theoretical Physics（亚太理论物理中心）；University of Potsdam（波茨坦大学）；Wakayama University（和歌山大学）；Nagoya University（名古屋大学）；Keio University（庆应义塾大学）
Ribbons are a class of slender structures whose length, width, and thickness are widely separated from each other. This scale separation gives a ribbon unusual mechanical properties in athermal macroscopic settings, e.g. it can bend without twisting, but cannot twist without bending. Given the ubiquity of ribbon-like biopolymers in biology and chemistry, here we study the statistical mechanics of microscopic inextensible, fluctuating ribbons loaded by forces and torques. We show that these ribbons exhibit a range of topologically and geometrically complex morphologies exemplified by three phas…
Two-dimensional colloidal suspensions exposed to periodic external fields exhibit a variety of molecular crystalline phases. There two or more colloids assemble at lattice sites of potential minima to build new structural entities, referred to as molecules. Using the strength of the potential and the filling fraction as control parameter, phase transition to unconventional orientationally ordered states can be induced. We introduce an approach that focuses at the discrete set of orientational states relevant for the phase ordering. The orientationally ordered states are mapped to classical spi…
We consider Langevin equation with dichotomously fluctuating diffusivity, where the diffusion coefficient changes dichotomously in time, in order to study fluctuations of time-averaged observables in temporary heterogeneous diffusion process. We find that occupation time statistics is a powerful tool for calculating the time-averaged mean square displacement in the model. We show that the time-averaged diffusion coefficients are intrinsically random when the mean sojourn time for one of the states diverges. Our model provides anomalous fluctuations of time-averaged diffusivity, which have rele…
We study the density of specular reflection points in the geometrical optics limit when light scatters off fluctuating interfaces and membranes in thermodynamic equilibrium. We focus on the statistical mechanics of both capillary-gravity interfaces (characterized by a surface tension) and fluid membranes (controlled by a bending rigidity) in thermodynamic equilibrium in two dimensions. Building on work by Berry, Nye, Longuet-Higgins and others, we show that the statistics of specular points is fully characterized by three fundamental length scales, namely, a correlation length $ξ$, a microscop…
We present a hybrid method for the simulation of colloidal systems, that combines molecular dynamics (MD) with the Lattice-Boltzmann (LB) scheme. The LB method is used as a model for the solvent in order to take into account the hydrodynamic mass and momentum transport through the solvent. The colloidal particles are propagated via MD and they are coupled to the LB fluid by viscous forces. With respect to the LB fluid, the colloids are represented by uniformly distributed points on a sphere. Each such point (with a velocity V(r) at any off-lattice position r is interacting with the neighboring…
An understanding of homogeneous nucleation of crystalline structure from a disordered medium such as a liquid remains an important unsolved problem in condensed matter physics. Guided by the results from a number of experiments on granular and colloidal systems in the past two decades, including in particular observations of homogeneous nucleation in colloidal and granular systems, we suggest an alternative to the statistical mechanics approach to static granular matter initiated by Edwards and Oakeshott in 1989.
Several statistical mechanical theories predict that colloidal suspensions of highly charged macroions and monovalent microions can exhibit unusual thermodynamic phase behavior when strongly deionized. Density-functional, extended Debye-Hückel, and response theories, within mean-field and linearization approximations, predict a spinodal phase instability of charged colloids below a critical salt concentration. Poisson-Boltzmann cell model studies of suspensions in Donnan equilibrium with a salt reservoir demonstrate that effective interactions and osmotic pressures predicted by such theories c…
We study the inverse problem of tuning interaction parameters between charged colloidal particles interacting with a hard-core repulsive Yukawa potential, so that they assemble into specified crystal structures. Here, we target the body-centered-cubic (bcc) structure which is only stable in a small region in the phase diagram of charged colloids and is, therefore, challenging to find. In order to achieve this goal, we use the statistical fluctuations in the bond orientational order parameters to tune the interaction parameters for the bcc structure, while initializing the system in the fluid p…
We present measurements of the thermal fluctuations of the free surface of an aging colloidal suspension, Laponite. The technique consists in measuring the fluctuations of the position of a laser beam that reflects from the free surface. Analysing the data statistics, we show that, as the fluid ages, the dynamics becomes intermittent. The intermittent events correspond to large changes in the local slope of the free surface over a few milliseconds. We show that those quakes are uncorrelated, although they are kept in memory by the surface over short time scales.
We rejuvenate well-aged quasi-2D binary colloidal glasses by thermal cycling, and systematically measure both the statistical responses and particle-level structural evolutions during rejuvenation. While the moduli and boson peak are continuously rejuvenated with increasing number of cycles, the mean square displacement (MSD) fluctuates significantly between different groups of thermal cycles. The decoupling between the thermodynamical and dynamical evolutions suggests different microscopic origins for different bulk properties of glasses. We find that a small fraction of structural rearrangem…
This work is devoted to the study of displacement fluctuations of micron-sized particles in an aging colloidal glass. We address the issue of the validity of the fluctuation dissipation theorem (FDT) and the time evolution of viscoelastic properties during aging of aqueous suspensions of a clay (Laponite RG) in a colloidal glass phase. Given the conflicting results reported in the literature for different experimental techniques, our goal is to check and reconcile them using \emph{simultaneously} passive and active microrheology techniques. For this purpose we measure the thermal fluctuations …
Ultrasoft colloidal particle fluctuates due to its flexibility. Such fluctuation is essential for colloidal structure and dynamics, but is challenging to quantify experimentally. We use dendrimers as a model system to study the fluctuation of ultrasoft colloids. By considering the dynamic polydispersity in the small-angle neutron scattering (SANS) model, and introducing the fluctuation of invasive water into the contrast in SANS, we reveal the fluctuating amplitudes of the size and shape of the dendrimer of generation 6 at finite concentrations. The size fluctuation is suppressed while the sha…
Unconventional Growth Kinetics and Fractal Interfaces of Colloidal Phase Separation in Active Liquids
Indian Institute of Science Education and Research Pune（印度科学教育研究所浦那分校）；Indian Institute of Technology (BHU) Varanasi（瓦拉纳西印度理工学院（贝拿勒斯印度教大学））；School of Physical Sciences, Jawaharlal Nehru University（贾瓦哈拉尔·尼赫鲁大学物理科学学院）
A statistical model of homopolymer DNA, coupling internal base pair states (unbroken or broken) and external thermal chain fluctuations, is exactly solved using transfer kernel techniques. The dependence on temperature and DNA length of the fraction of denaturation bubbles and their correlation length is deduced. The thermal denaturation transition emerges naturally when the chain fluctuations are integrated out and is driven by the difference in bending (entropy dominated) free energy between broken and unbroken segments. Conformational properties of DNA, such as persistence length and mean-s…
The Casimir and electromagnetic interactions between objects at short separations are strongly influenced by the local geometry near the point of closest approach. In this paper we demonstrate that the assumptions underlying common statistical analysis of roughness may not hold in experiments using micro-spheres as interacting objects. Based on an extensive experimental and numerical analysis of the surface topology of the widely used colloidal particle types 4310A and 4320A, we show that the actual variation in the local surface curvature may give rise to large uncertainties in the comparison…
By analysis and simulation we demonstrate two methods for achieving complete orientational alignment of a set of identical, asymmetric colloidal objects dispersed randomly in a fluid. Sedimentation or electrophoresis in a constant field can lead to partial alignment, in which the objects rotate about a common body axis, but the phases of rotation for these objects are random. We show that this phase disorder can be removed by two forms of programmed forcing. First, simply alternating the forcing between two directions reduces the statistical entropy of the orientation arbitrarily. Second, addi…
We propose a mathematical model to describe the athermal fluctuations of thin sheets driven by the type of random driving that might be experienced prior to weak crumpling. The model is obtained by merging the Föppl-von Kármán equations from elasticity theory with techniques from out-of-equilibrium statistical physics to obtain a nonlinear strongly coupled $ϕ^{4}$-Langevin field equation with spatially varying kernel. With the aid of the self-consistent expansion (SCE), this equation is analytically solved for the structure factor of a fluctuating sheet. In contrast to previous research which …
We study the effect of solvent granularity on the effective force between two charged colloidal particles by computer simulations of the primitive model of strongly asymmetric electrolytes with an explicitly added hard sphere solvent. Apart from molecular oscillating forces for nearly touching colloids which arise from solvent and counterion layering, the counterions are attracted towards the colloidal surfaces by solvent depletion providing a simple statistical description of hydration. This, in turn, has an important influence on the effective forces for larger distances which are considerab…
Active fluids comprise a variety of systems composed of elements immersed in a fluid environment which can convert some form of energy into directed motion; as such they are intrinsically out-of-equilibrium in the absence of any external forcing. A fundamental problem in the physics of active matter concerns the understanding of how the characteristics of the autonomous propulsion and agent-agent interactions determine the collective dynamics of the system. We study numerically suspensions of self-propelled diffusiophoretic colloids, in (quasi)-2d configurations, accounting for both dynamicall…
Colloidal bodies of irregular shape rotate as they descend under gravity in solution. This rotational response provides a means of bringing a dispersion of identical bodies into a synchronized rotation with the same orientation using programmed forcing. We use the notion of statistical entropy to derive bounds on the rate of synchronization. These bounds apply generally to dynamical systems with stable periodic motion with a phase $ϕ(t)$, when subjected to an impulsive perturbation. The impulse causes a change of phase expressible as a phase map $ψ(ϕ)$. We derive an upper limit on the average …
Fluctuations in fluid velocity and fluctuations in electric fields may both give rise to forces acting on small particles in colloidal suspensions. Such forces in part determine the thermodynamic stability of the colloid. At the classical statistical thermodynamic level, the fluid velocity and electric field contributions to the forces are comparable in magnitude. When quantum fluctuation effects are taken into account, the electric fluctuation induced van der Waals forces dominate those induced by purely fluid mechanical motions. The physical principles are applied in detail for the case of c…
Application of integral equation theory to complex fluids is reviewed, with particular emphasis to the effects of polydispersity and anisotropy on their structural and thermodynamic properties. Both analytical and numerical solutions of integral equations are discussed within the context of a set of minimal potential models that have been widely used in the literature. While other popular theoretical tools, such as numerical simulations and density functional theory, are superior for quantitative and accurate predictions, we argue that integral equation theory still provides, as in simple flui…
For biologically relevant macromolecules such as intrinsically disordered proteins, internal degrees of freedom that allow for shape changes have a large influence on both the motion and function of the compound. A detailed understanding of the effect of flexibility is needed in order to explain their behavior. Here, we study a model system of freely-jointed chains of three to six colloidal spheres, using both simulations and experiments. We find that in spite of their short lengths, their conformational statistics are well described by two-dimensional Flory theory, while their average transla…
