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Domain decay is at the heart of the so-called evaporation-condensation Ostwald-ripening regime of phase ordering kinetics, where the growth of large domains occurs at the expense of smaller ones, which are expected to `evaporate'. We experimentally investigate such decay dynamics at the level of a single spherical domain picked from one phase in coexistence and brought into the other phase by an opto-mechanical approach, in a near-critical phase-separated binary liquid mixture. We observe that the decay dynamics is generally not compatible with the theoretically expected surface-tension decay laws for conserved order parameters. Using a mean-field description, we quantitatively explain this apparent disagreement by the gradient of solute concentrations induced by gravity close to a critical point. Finally, we determine the conditions for which buoyancy becomes negligible compared to capillarity and perform dedicated experiments that retrieve the predicted surface-tension induced decay exponent. The surface-tension driven decay dynamics of conserved order parameter systems in the presence and the absence of gravity, is thus established at the level of a single domain., Comment: 4 pages (main text) + 8 pages (SM); Accepted in PRL

In this chapter, we consider the problem of a non-Markovian random walker (displaying memory effects) searching for a target. We review an approach that links the first passage statistics to the properties of trajectories followed by the random walker in the future of the first passage time. This approach holds in one and higher spatial dimensions, when the dynamics in the vicinity of the target is Gaussian, and it is applied to three paradigmatic target search problems: the search for a target in confinement, the search for a rarely reached configuration (rare event kinetics), or the search for a target in infinite space, for processes featuring stationary increments or transient aging. The theory gives access to the mean first passage time (when it exists) or to the behavior of the survival probability at long times, and agrees with the available exact results obtained perturbatively for examples of weakly non-Markovian processes. This general approach reveals that the characterization of the non-equilibrium state of the system at the instant of first passage is key to derive first-passage kinetics, and provides a new methodology, via the analysis of trajectories after the first-passage, to make it quantitative., Comment: 22 pages, invited chapter for the book "The Target Problem" (Eds. D. S. Grebenkov, R. Metzler, G. Oshanin)

We study the diffusion of particles confined close to a single wall and in double-wall planar channel geometries where the local diffusivities depend on the distance to the boundaries. Displacement parallel to the walls is Brownian as characterized by its variance, but it is non-Gaussian having a non-zero fourth cumulant. Establishing a link with Taylor dispersion, we calculate the fourth cumulant and the tails of the displacement distribution for general diffusivity tensors along with potentials generated by either the walls or externally, for instance gravity. Experimental and numerical studies of the motion of a colloid in the direction parallel to the wall give measured fourth cumulants which are correctly predicted by our theory. Interestingly, contrary to models of Brownian-yet-non-Gaussian diffusion, the tails of the displacement distribution are shown to be Gaussian rather than exponential. All together, our results provide additional tests and constraints for the inference of force maps and local transport properties near surfaces.

The paradigmatic model for heterogeneous media used in diffusion studies is built from reflecting obstacles and surfaces. It is well known that the crowding effect produced by these reflecting surfaces slows the dispersion of Brownian tracers. Here, using a general adsorption desorption model with surface diffusion, we show analytically that making surfaces or obstacles attractive can accelerate dispersion. In particular, we show that this enhancement of diffusion can exist even when the surface diffusion constant is smaller than that in the bulk. Even more remarkably, this enhancement effect occurs when the effective diffusion constant, when restricted to surfaces only, is lower than the effective diffusivity with purely reflecting boundaries. We give analytical formulas for this intriguing effect in periodic arrays of spheres as well as undulating micro-channels. Our results are confirmed by numerical calculations and Monte Carlo simulations.

Chemical reactions generically require that particles come into contact. In practice, reaction is often imperfect and can necessitate multiple random encounters between reactants. In confined geometries, despite notable recent advances, there is to date no general analytical treatment of such imperfect transport-limited reaction kinetics. Here, we determine the kinetics of imperfect reactions in confining domains for any diffusive or anomalously diffusive Markovian transport process, and for different models of imperfect reactivity. We show that the full distribution of reaction times is obtained in the large confining volume limit from the knowledge of the mean reaction time only, which we determine explicitly. This distribution for imperfect reactions is found to be identical to that of perfect reactions upon an appropriate rescaling of parameters, which highlights the robustness of our results. Strikingly, this holds true even in the regime of low reactivity where the mean reaction time is independent of the transport process, and can lead to large fluctuations of the reaction time even in simple reaction schemes. We illustrate our results for normal diffusion in domains of generic shape, and for anomalous diffusion in complex environments, where our predictions are confirmed by numerical simulations., Comment: to appear in Communications Chemistry

We consider Taylor dispersion for tracer particles in micro-fluidic planar channels with strong confinement. In this context, the channel walls modify the local diffusivity tensor and also interactions between the tracer particles and the walls become important. We provide a simple and general formula for the effective diffusion constant along the channel as well as the first non-trivial finite time correction for arbitrary flows along the channel, arbitrary interaction potentials with the walls and arbitrary expressions for the diffusion tensor. The formula are in particular amenable to a straightforward numerical implementation, rendering them extremely useful for comparison with experiments. We present a number of applications, notably for systems which have parabolically varying diffusivity profiles, to systems with attractive interactions with the walls as well as electroosmotic flows between plates with differing surface charges within the Debye-H\"uckel approximation., Comment: 33 pages, 7 figures

How much time does it take for a fluctuating system, such as a polymer chain, to reach a target configuration that is rarely visited -- typically because of a high energy cost ? This question generally amounts to the determination of the first-passage time statistics to a target zone in phase space with lower occupation probability. Here, we present an analytical method to determine the mean first-passage time of a generic non-Markovian random walker to a rarely visited threshold, which goes beyond existing weak-noise theories. We apply our method to polymer systems, to determine (i) the first time for a flexible polymer to reach a large extension, and (ii) the first closure time of a stiff inextensible wormlike chain. Our results are in excellent agreement with numerical simulations and provide explicit asymptotic laws for the mean first-passage times to rarely visited configurations., Comment: Accepted in Physical Review Research (Rapid Communication) Main text + SI

We consider a model of a particle trapped in a harmonic optical trap but with the addition of a non-conservative radiation induced force. This model is known to correctly describe experimentally observed trapped particle statistics for a wide range of physical parameters such as temperature and pressure. We theoretically analyse the effect of non-conservative force on the underlying steady state distribution as well as the power spectrum for the particle position. We compute perturbatively the probability distribution of the resulting non-equilibrium steady states for all dynamical regimes, underdamped through to overdamped and give expressions for the associated currents in phase space (position and velocity). We also give the spectral density of the trapped particle's position in all dynamical regimes and for any value of the non-conservative force. Signatures of the presence non-conservative forces are shown to be particularly strong for in the underdamped regime at low frequencies., Comment: 25 pages, 5 figures

As a first approximation, the forces acting on optically trapped particles are commonly assumed to be conservative. The influence of the nonconservative force has been shown to be negligible in overdamped liquid environments. However, its impact in the underdamped regime remains unexplored. Here, we experimentally study the combined effects of gradient and scattering forces on the nonlinear dynamics of trapped particles at various air pressures, leading to significant low-frequency noise excess along the optical axis and the emergence of toroidal Brownian vortices. Our results supported, by numerical simulations and a theoretical model, provide fundamental insights into the functioning of optical tweezers and a means for investigating nonequilibrium steady states in the presence of nonconservative forces.

This paper presents a theoretical analysis of the closure kinetics of a polymer with hydrodynamic interactions. This analysis, which takes into account the non-Markovian dynamics of the end-to-end vector and relies on the preaveraging of the mobility tensor (Zimm dynamics), is shown to reproduce very accurately the results of numerical simulations of the complete non linear dynamics. It is found that Markovian treatments, based on a Wilemski-Fixman approximation, significantly overestimate cyclization times (up to a factor 2), showing the importance of memory effects in the dynamics. In addition, this analysis provides scaling laws of the mean first cyclization time (MFCT) with the polymer size $N$ and capture radius $b$, which are identical in both Markovian and non-Markovian approaches. In particular, it is found that the scaling of the MFCT for large $N$ is given by $T\sim N^{3/2}\ln (N/b^2)$, which differs from the case of the Rouse dynamics where $T\sim N^{2}$. The extension to the case of the reaction kinetics of a monomer of a Zimm polymer with an external target in a confined volume is also presented.

We study the dynamics of local bond orientation in regular hyperbranched polymers modeled by Vicsek fractals. The local dynamics is investigated through the temporal autocorrelation functions of single bonds and the corresponding relaxation forms of the complex dielectric susceptibility. We show that the dynamic behavior of single segments depends on their remoteness from the periphery rather than on the size of the whole macromolecule. Remarkably, the dynamics of the core segments (which are most remote from the periphery) shows a scaling behavior that differs from the dynamics obtained after structural average. We analyze the most relevant processes of single segment motion and provide an analytic approximation for the corresponding relaxation times. Furthermore, we describe an iterative method to calculate the orientational dynamics in the case of very large macromolecular sizes., Comment: 11 pages, 9 figures

We consider the kinetics of first contact between two monomers of the same macromolecule. Relying on a fractal description of the macromolecule, we develop an analytical method to compute the Mean First Contact Time (MFCT) for various molecular sizes. In our theoretical description, the non-Markovian feature of monomer motion, arising from the interactions with the other monomers, is captured by accounting for the non-equilibrium conformations of the macromolecule at the very instant of first contact. This analysis reveals a simple scaling relation for the MFCT between two monomers, which involves only their equilibrium distance and the spectral dimension of the macromolecule, independently of its microscopic details. Our theoretical predictions are in excellent agreement with numerical stochastic simulations.

The effect of a constant applied external force, induced for instance by an electric or gravitational field, on the dispersion of Brownian particles in periodic media with spatially varying diffusivity, and thus mobility, is studied. We show that external forces can greatly enhance dispersion in the direction of the applied force and also modify, to a lesser extent and in some cases non-monotonically, dispersion perpendicular to the applied force. Our results thus open up the intriguing possibility of modulating the dispersive properties of heterogeneous media by using externally applied force fields. These results are obtained via a Kubo formula which can be applied to any periodic advection diffusion system in any spatial dimension., Comment: Main text (4 pages, 2 figures) + Supplemental Material (4 pages)

We analyze the mean squared displacement of a Brownian particle in a medium with a spatially varying local diffusivity which is assumed to be periodic. When the system is asymptotically diffusive the mean squared displacement, characterizing the dispersion in the system, is, at late times, a linear function of time. A Kubo type formula is given for the mean squared displacement which allows the recovery of some known results for the effective diffusion constant $D_e$ in a direct way, but also allows an understanding of the asymptotic approach to the diffusive limit. In particular, as well as as computing the slope of a linear fit to the late time mean squared displacement, we find a formula for the constant where the fit intersects the y axis., Comment: 8 pages, 2 figures, revtex

Describing the kinetics of polymer reactions, such as the formation of loops and hairpins in nucleic acids or polypeptides, is complicated by the structural dynamics of their chains. Although both intramolecular reactions, such as cyclization, and intermolecular reactions have been studied extensively, both experimentally and theoretically, there is to date no exact explicit analytical treatment of transport-limited polymer reaction kinetics, even in the case of the simplest (Rouse) model of monomers connected by linear springs. We introduce a new analytical approach to calculate the mean reaction time of polymer reactions that encompasses the non-Markovian dynamics of monomer motion. This requires that the conformational statistics of the polymer at the very instant of reaction be determined, which provides, as a by-product, new information on the reaction path. We show that the typical reactive conformation of the polymer is more extended than the equilibrium conformation, which leads to reaction times significantly shorter than predicted by the existing classical Markovian theory., Comment: Main text (7 pages, 5 figures) + Supplemantary Information (13 pages, 2 figures)