Ultra-Slow Vacancy-Mediated Tracer Diffusion in Two Dimensions: The Einstein Relation Verified

We study the dynamics of a charged tracer particle (TP) on a two-dimensional lattice all sites of which except one (a vacancy) are filled with identical neutral, hard-core particles. The particles move randomly by exchanging their positions with the vacancy, subject to the hard-core exclusion. In case when the charged TP experiences a bias due to external electric field ${\bf E}$, (which favors its jumps in the preferential direction), we determine exactly the limiting probability distribution of the TP position in terms of appropriate scaling variables and the leading large-N ($n$ being the discrete time) behavior of the TP mean displacement $\bar{{\bf X}}_n$; the latter is shown to obey an anomalous, logarithmic law $|\bar{{\bf X}}_n| = \alpha_0(|{\bf E}|) \ln(n)$. On comparing our results with earlier predictions by Brummelhuis and Hilhorst (J. Stat. Phys. {\bf 53}, 249 (1988)) for the TP diffusivity $D_n$ in the unbiased case, we infer that the Einstein relation $\mu_n = \beta D_n$ between the TP diffusivity and the mobility $\mu_n = \lim_{|{\bf E}| \to 0}(|\bar{{\bf X}}_n|/| {\bf E} |n)$ holds in the leading in $n$ order, despite the fact that both $D_n$ and $\mu_n$ are not constant but vanish as $n \to \infty$. We also generalize our approach to the situation with very small but finite vacancy concentration $\rho$, in which case we find a ballistic-type law $|\bar{{\bf X}}_n| = \pi \alpha_0(|{\bf E}|) \rho n$. We demonstrate that here, again, both $D_n$ and $\mu_n$, calculated in the linear in $\rho$ approximation, do obey the Einstein relation.Comment: 25 pages, one figure, TeX, submitted to J. Stat. Phy

Kinetics of active surface-mediated diffusion in spherically symmetric domains

We present an exact calculation of the mean first-passage time to a target on the surface of a 2D or 3D spherical domain, for a molecule alternating phases of surface diffusion on the domain boundary and phases of bulk diffusion. We generalize the results of [J. Stat. Phys. {\bf 142}, 657 (2011)] and consider a biased diffusion in a general annulus with an arbitrary number of regularly spaced targets on a partially reflecting surface. The presented approach is based on an integral equation which can be solved analytically. Numerically validated approximation schemes, which provide more tractable expressions of the mean first-passage time are also proposed. In the framework of this minimal model of surface-mediated reactions, we show analytically that the mean reaction time can be minimized as a function of the desorption rate from the surface.Comment: Published online in J. Stat. Phy

Reactive conformations and non-Markovian reaction kinetics of a Rouse polymer searching for a target in confinement

We investigate theoretically a diffusion-limited reaction between a reactant attached to a Rouse polymer and an external fixed reactive site in confinement. The present work completes and goes beyond a previous study [T. Gu\'erin, O. B\'enichou and R. Voituriez, Nat. Chem., 4, 268 (2012)] that showed that the distribution of the polymer conformations at the very instant of reaction plays a key role in the reaction kinetics, and that its determination enables the inclusion of non-Markovian effects in the theory. Here, we describe in detail this non-Markovian theory and we compare it with numerical stochastic simulations and with a Markovian approach, in which the reactive conformations are approximated by equilibrium ones. We establish the following new results. Our analysis reveals a strongly non-Markovian regime in 1D, where the Markovian and non-Markovian dependance of the relation time on the initial distance are different. In this regime, the reactive conformations are so different from equilibrium conformations that the Markovian expressions of the reaction time can be overestimated by several orders of magnitudes for long chains. We also show how to derive qualitative scaling laws for the reaction time in a systematic way that takes into account the different behaviors of monomer motion at all time and length scales. Finally, we also give an analytical description of the average elongated shape of the polymer at the instant of the reaction and we show that its spectrum behaves a a slow power-law for large wave numbers

Convex hull of a Brownian motion in confinement

We study the effect of confinement on the mean perimeter of the convex hull of a planar Brownian motion, defined as the minimum convex polygon enclosing the trajectory. We use a minimal model where an infinite reflecting wall confines the walk to its one side. We show that the mean perimeter displays a surprising minimum with respect to the starting distance to the wall and exhibits a non-analyticity for small distances. In addition, the mean span of the trajectory in a fixed direction {$\theta \in ]0,\pi/2[$}, which can be shown to yield the mean perimeter by integration over $\theta$, presents these same two characteristics. This is in striking contrast with the one dimensional case, where the mean span is an increasing analytical function. The non-monotonicity in the 2D case originates from the competition between two antagonistic effects due to the presence of the wall: reduction of the space accessible to the Brownian motion and effective repulsion