Bulk Mediated Surface Diffusion: The Infinite System Case

Recently, the intrinsic sampling method has been developed in order to obtain, from molecular simulations, the intrinsic structure of the liquid-vapor interface that is presupposed in the classical capillary wave theory. Our purpose here is to study dynamical processes at the liquid-vapor interface, since this method allows tracking down and analyzing the movement of surface molecules, thus providing, with great accuracy, dynamical information on molecules that are "at" the i...

The escape dynamics of sticky particles from textured surfaces is poorly understood despite importance to various scientific and technological domains. In this work, we address this challenge by investigating the escape time of adsorbates from prevalent surface topographies, including holes/pits, pillars, and grooves. Analytical expressions for the probability density function and the mean of the escape time are derived. A particularly interesting scenario is that of very dee...

A simple multiscale approach to the diffusion-driven adsorption from a solution to a solid surface is presented. The model combines two important features of the adsorption process: (i) the kinetics of the chemical reaction between adsorbing molecules and the surface; and (ii) geometrical constraints on the surface made by molecules which are already adsorbed. The process (i) is modelled in a diffusion-driven context, i.e. the conditional probability of adsorbing a molecule p...

A quantitative model of the mobility of functionalized particles at the interface is pivotal to understanding important systems in biology and nanotechnology. In this work, we investigate the emerging dynamics of particles anchored through ligand-receptor bridges to functionalized surfaces. We consider systems with reversible bridges in which ligand-receptor pairs bind/unbind with finite reaction rates. For a given set of bridges, the particle can explore a tiny fraction of t...

A new solution to the mono-dimensional diffusion equation for time-variable first kind boundary condition is presented where the time-variable function at the surface is derived proposing a surface saturation model. This solution may be helpful in the treatment of diffusion processes where the overall time of diffusion is comparable with the time taken by the surface of the solid body to saturate achieving a dynamical equilibrium between the diffusing elements supplied by the...

Extensive numerical simulation are reported for the structure and dynamics of large clusters on metal(100) surfaces. Different types of perimeter hopping processes makes center-of-mass of the cluster to follow a a random walk trajectory. Then, a {\it diffusion coefficient} $D$ can be defined as $\lim\limits_{t\to \infty} D(t)$, with $D(t)=< d^2 >/(4t)$ and $d$ the displacement of the center-of-mass. In the simulations, the dependence of the diffusion coefficient on those peri...

A theory based on the thermodynamic Gibbs-Thomson relation is presented which provides the framework for understanding the time evolution of isolated nanoscale features (i.e., islands and pits) on surfaces. Two limiting cases are predicted, in which either diffusion or interface transfer is the limiting process. These cases correspond to similar regimes considered in previous works addressing the Ostwald ripening of ensembles of features. A third possible limiting case is not...

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 e...

Adsorption is the accumulation of a solute at an interface that is formed between a solution and an additional gas, liquid, or solid phase. The macroscopic theory of adsorption dates back more than a century and is now well-established. Yet, despite recent advancements, a detailed and self-contained theory of single-particle adsorption is still lacking. Here, we bridge this gap by developing a microscopic theory of adsorption kinetics, from which the macroscopic properties fo...

A physical-mathematical approach to anomalous diffusion may be based on fractional diffusion equations and related random walk models. The fundamental solutions of these equations can be interpreted as probability densities evolving in time of peculiar self-similar stochastic processes: an integral representation of these solutions is here presented. A more general approach to anomalous diffusion is known to be provided by the master equation for a continuous time random walk...