Field-driven tracer diffusion through curved bottlenecks: fine structure of first passage events.

Using scaling arguments and extensive numerical simulations, we study the dynamics of a tracer particle in a corrugated channel represented by a periodic sequence of broad chambers and narrow funnel-like bottlenecks enclosed by a hard-wall boundary. The tracer particle is affected by an external force pointing along the channel, and performs an unbiased diffusion in the perpendicular direction. We present a detailed analysis (a) of the distribution function of the height above the funnel's boundary at which the first crossing of a given bottleneck takes place, and (b) of the distribution function of the first passage time to such an event. Our analysis reveals several new features of the dynamical behaviour that are overlooked in the studies based on the Fick-Jacobs approach. In particular, trajectories passing through a funnel concentrate predominantly on its boundary, which makes first-crossing events very sensitive to the presence of binding sites and microscopic roughness.

Tracer diffusion in crowded narrow channels.

We summarise different results on the diffusion of a tracer particle in lattice gases of hard-core particles with stochastic dynamics, which are confined to narrow channels-single-files, comb-like structures and quasi-one-dimensional channels with the width equal to several particle diameters. We show that in such geometries a surprisingly rich, sometimes even counter-intuitive, behaviour emerges, which is absent in unbounded systems. This is well-documented for the anomalous diffusion in single-files. Less known is the anomalous dynamics of a tracer particle in crowded branching single-files-comb-like structures, where several kinds of anomalous regimes take place. In narrow channels, which are broader than single-files, one encounters a wealth of anomalous behaviours in the case where the tracer particle is subject to a regular external bias: here, one observes an anomaly in the temporal evolution of the tracer particle velocity, super-diffusive at transient stages, and ultimately a giant diffusive broadening of fluctuations in the position of the tracer particle, as well as spectacular multi-tracer effects of self-clogging of narrow channels. Interactions between a biased tracer particle and a confined crowded environment also produce peculiar patterns in the out-of-equilibrium distribution of the environment particles, very different from the ones appearing in unbounded systems. For moderately dense systems, a surprising effect of a negative differential mobility takes place, such that the velocity of a biased tracer particle can be a non-monotonic function of the force. In some parameter ranges, both the velocity and the diffusion coefficient of a biased tracer particle can be non-monotonic functions of the density. We also survey different results obtained for a tracer particle diffusion in unbounded systems, which will permit a reader to have an exhaustively broad picture of the tracer diffusion in crowded environments.

Nonlinear response and emerging nonequilibrium microstructures for biased diffusion in confined crowded environments.

We study analytically the dynamics and the microstructural changes of a host medium caused by a driven tracer particle moving in a confined, quiescent molecular crowding environment. Imitating typical settings of active microrheology experiments, we consider here a minimal model comprising a geometrically confined lattice system (a two-dimensional striplike or a three-dimensional capillary-like system) populated by two types of hard-core particles with stochastic dynamics (a tracer particle driven by a constant external force and bath particles moving completely at random). Resorting to a decoupling scheme, which permits us to go beyond the linear-response approximation (Stokes regime) for arbitrary densities of the lattice gas particles, we determine the force-velocity relation for the tracer particle and the stationary density profiles of the host medium particles around it. These results are validated a posteriori by extensive numerical simulations for a wide range of parameters. Our theoretical analysis reveals two striking features: (a) We show that, under certain conditions, the terminal velocity of the driven tracer particle is a nonmonotonic function of the force, so in some parameter range the differential mobility becomes negative, and (b) the biased particle drives the whole system into a nonequilibrium steady state with a stationary particle density profile past the tracer, which decays exponentially, in sharp contrast with the behavior observed for unbounded lattices, where an algebraic decay is known to take place.

Diffusion and Subdiffusion of Interacting Particles on Comblike Structures.

We study the dynamics of a tracer particle (TP) on a comb lattice populated by randomly moving hard-core particles in the dense limit. We first consider the case where the TP is constrained to move on the backbone of the comb only. In the limit of high density of the particles, we present exact analytical results for the cumulants of the TP position, showing a subdiffusive behavior ∼t^{3/4}. At longer times, a second regime is observed where standard diffusion is recovered, with a surprising nonanalytical dependence of the diffusion coefficient on the particle density. When the TP is allowed to visit the teeth of the comb, based on a mean-field-like continuous time random walk description, we unveil a rich and complex scenario with several successive subdiffusive regimes, resulting from the coupling between the geometrical constraints of the comb lattice and particle interactions. In this case, remarkably, the presence of hard-core interactions asymptotically speeds up the TP motion along the backbone of the structure.

Microscopic theory for negative differential mobility in crowded environments.

We study the behavior of the stationary velocity of a driven particle in an environment of mobile hard-core obstacles. Based on a lattice gas model, we demonstrate analytically that the drift velocity can exhibit a nonmonotonic dependence on the applied force, and show quantitatively that such negative differential mobility (NDM), observed in various physical contexts, is controlled by both the density and diffusion time scale of the obstacles. Our study unifies recent numerical and analytical results obtained in specific regimes, and makes it possible to determine analytically the region of the full parameter space where NDM occurs. These results suggest that NDM could be a generic feature of biased (or active) transport in crowded environments.

Active transport in dense diffusive single-file systems.

We study a minimal model of active transport in crowded single-file environments which generalizes the emblematic model of single-file diffusion to the case when the tracer particle (TP) performs either an autonomous directed motion or is biased by an external force, while all other particles of the environment (bath) perform unbiased diffusions. We derive explicit expressions, valid in the limit of high density of bath particles, of the full distribution P((n))(X) of the TP position and of all its cumulants, for arbitrary values of the bias f and for any time n. Our analysis reveals striking features, such as the anomalous scaling [proportionality] √[n] of all cumulants, the equality of cumulants of the same parity characteristic of a Skellam distribution and a convergence to a Gaussian distribution in spite of asymmetric density profiles of bath particles. Altogether, our results provide the full statistics of the TP position and set the basis for a refined analysis of real trajectories of active particles in crowded single-file environments.

Precursor films in wetting phenomena.

The spontaneous spreading of non-volatile liquid droplets on solid substrates poses a classic problem in the context of wetting phenomena. It is well known that the spreading of a macroscopic droplet is in many cases accompanied by a thin film of macroscopic lateral extent, the so-called precursor film, which emanates from the three-phase contact line region and spreads ahead of the latter with a much higher speed. Such films have been usually associated with liquid-on-solid systems, but in the last decade similar films have been reported to occur in solid-on-solid systems. While the situations in which the thickness of such films is of mesoscopic size are fairly well understood, an intriguing and yet to be fully understood aspect is the spreading of microscopic, i.e. molecularly thin, films. Here we review the available experimental observations of such films in various liquid-on-solid and solid-on-solid systems, as well as the corresponding theoretical models and studies aimed at understanding their formation and spreading dynamics. Recent developments and perspectives for future research are discussed.

Symmetry breaking between statistically equivalent, independent channels in few-channel chaotic scattering.

We study the distribution function P(ω) of the random variable ω=τ(1)/(τ(1)+···+τ(N)), where τ(k)'s are the partial Wigner delay times for chaotic scattering in a disordered system with N independent, statistically equivalent channels. In this case, τ(k)'s are independent and identically distributed random variables with a distribution Ψ(τ) characterized by a "fat" power-law intermediate tail ~1/τ(1+µ), truncated by an exponential (or a log-normal) function of τ. For N=2 and N=3, we observe a surprisingly rich behavior of P(ω), revealing a breakdown of the symmetry between identical independent channels. For N=2, numerical simulations of the quasi-one-dimensional Anderson model confirm our findings.

Narrow-escape times for diffusion in microdomains with a particle-surface affinity: mean-field results.

We analyze the mean time t(app) that a randomly moving particle spends in a bounded domain (sphere) before it escapes through a small window in the domain's boundary. A particle is assumed to diffuse freely in the bulk until it approaches the surface of the domain where it becomes weakly adsorbed, and then wanders diffusively along the boundary for a random time until it desorbs back to the bulk, etc. Using a mean-field approximation, we define t(app) analytically as a function of the bulk and surface diffusion coefficients, the mean time it spends in the bulk between two consecutive arrivals to the surface and the mean time it wanders on the surface within a single round of the surface diffusion.

Survival of an evasive prey.

We study the survival of a prey that is hunted by N predators. The predators perform independent random walks on a square lattice with V sites and start a direct chase whenever the prey appears within their sighting range. The prey is caught when a predator jumps to the site occupied by the prey. We analyze the efficacy of a lazy, minimal-effort evasion strategy according to which the prey tries to avoid encounters with the predators by making a hop only when any of the predators appears within its sighting range; otherwise the prey stays still. We show that if the sighting range of such a lazy prey is equal to 1 lattice spacing, at least 3 predators are needed in order to catch the prey on a square lattice. In this situation, we establish a simple asymptotic relation ln P(ev)(t) approximately (N/V)(2)ln P(imm)(t) between the survival probabilities of an evasive and an immobile prey. Hence, when the density rho = N/V of the predators is low, rho << 1, the lazy evasion strategy leads to the spectacular increase of the survival probability. We also argue that a short-sighting prey (its sighting range is smaller than the sighting range of the predators) undergoes an effective superdiffusive motion, as a result of its encounters with the predators, whereas a far-sighting prey performs a diffusive-type motion.

Confinement effects on diffusiophoretic self-propellers.

We study theoretically the effects of spatial confinement on the phoretic motion of a dissolved particle driven by composition gradients generated by chemical reactions of their solvent, which are active only on certain parts of the particle surface. We show that the presence of confining walls increases in a similar way both the composition gradients and the viscous friction, and the overall result of these competing effects is an increase in the phoretic velocity of the particle. For the case of steric repulsion only between the particle and the product molecules of the chemical reactions, the absolute value of the velocity remains nonetheless rather small.

Post-Tanner stages of droplet spreading: the energy balance approach revisited.

The spreading of a circular liquid drop on a solid substrate can be described in terms of the time evolution of its base radius R(t). In complete wetting, the quasistationary regime (far away from initial and final transients) typically obeys the so-called Tanner law, with R∼t(α(T)), α(T) = 1/10. Late-time spreading may differ significantly from the Tanner law: in some cases the drop does not thin down to a molecular film and instead reaches an equilibrium pancake-like shape; in other situations, as revealed by recent experiments with spontaneously spreading nematic crystals, the growth of the base radius accelerates after the Tanner stage. Here we demonstrate that these two seemingly conflicting trends can be reconciled within a suitably revisited energy balance approach, by taking into account the line tension contribution to the driving force of spreading: a positive line tension is responsible for the formation of pancake-like structures, whereas a negative line tension tends to lengthen the contact line and induces an accelerated spreading (a transition to a faster power law for R(t) than in the Tanner stage).

Post-Tanner spreading of nematic droplets.

The quasistationary spreading of a circular liquid drop on a solid substrate typically obeys the so-called Tanner law, with the instantaneous base radius R(t) growing with time as R∼t(1/10)-an effect of the dominant role of capillary forces for a small-sized droplet. However, for droplets of nematic liquid crystals, a faster spreading law sets in at long times, so that R∼t(α) with α significantly larger than the Tanner exponent 1/10. In the framework of the thin film model (or lubrication approximation), we describe this 'acceleration' as a transition to a qualitatively different spreading regime driven by a strong substrate-liquid interaction specific to nematics (antagonistic anchoring at the interfaces). The numerical solution of the thin film equation agrees well with the available experimental data for nematics, even though the non-Newtonian rheology has yet to be taken into account. Thus we complement the theory of spreading with a post-Tanner stage, noting that the spreading process can be expected to cross over from the usual capillarity-dominated stage to a regime where the whole reservoir becomes a diffusive film in the sense of Derjaguin.

Survival probability of a particle in a sea of mobile traps: a tale of tails.

We study the long-time tails of the survival probability P(t) of an A particle diffusing in d-dimensional media in the presence of a concentration rho of traps B that move subdiffusively, such that the mean square displacement of each trap grows as tgamma with 0 < or = gamma < or =1. Starting from a continuous time random walk description of the motion of the particle and of the traps, we derive lower and upper bounds for P(t) and show that for gamma < or =2/(d+2) these bounds coincide asymptotically, thus determining asymptotically exact results. The asymptotic decay law in this regime is exactly that obtained for immobile traps. This means that for sufficiently subdiffusive traps, the moving A particle sees the traps as essentially immobile, and Lifshitz or trapping tails remain unchanged. For gamma >2/(d+2) and d< or =2 the upper and lower bounds again coincide, leading to a decay law equal to that of a stationary particle. Thus, in this regime the moving traps see the particle as essentially immobile. For d>2 , however, the upper and lower bounds in this gamma regime no longer coincide, and the decay law for the survival probability of the A particle remains ambiguous.

Exact asymptotics for nonradiative migration-accelerated energy transfer in one-dimensional systems.

We study direct energy transfer by multipolar or exchange interactions between diffusive excited donor and diffusive unexcited acceptors. Extending over the case of long-range transfer of an excitation energy a nonperturbative approach by Bray and Blythe [Phys. Rev. Lett. 89, 150601 (2002)], originally developed for contact diffusion-controlled reactions, we determine exactly long-time asymptotics of the donor decay function in one-dimensional systems.

Kinetics of diffusion-limited catalytically activated reactions: an extension of the Wilemski-Fixman approach.

We study the kinetics of diffusion-limited catalytically activated A+B-->B reactions taking place in three-dimensional systems, in which an annihilation of diffusive A particles by diffusive traps B may happen only if the encounter of an A with any of the Bs happens within a special catalytic subvolumen: these subvolumens being immobile and uniformly distributed within the reaction bath. Suitably extending the classical approach of Wilemski and Fixman [J. Chem. Phys. 58, 4009 (1973)] to such three-molecular diffusion-limited reactions, we calculate analytically an effective reaction constant and show that it comprises several terms associated with the residence and joint residence times of Brownian paths in finite domains. The effective reaction constant exhibits a nontrivial dependence on the reaction radii, the mean density of catalytic subvolumens, and particles' diffusion coefficients. Finally, we discuss the fluctuation-induced kinetic behavior in such systems.

Corrections to the law of mass action and properties of the asymptotic t=infinity state for reversible diffusion-limited reactions.

For diffusion-limited reversible A+A<==>B reactions we reexamine two fundamental concepts of classical chemical kinetics-the notion of "chemical equilibrium" and the "law of mass action." We consider a general model with distance-dependent reaction rates, such that any pair of A particles, performing standard random walks on sites of a d-dimensional lattice and being at a distance mu apart of each other at time moment t, may associate forming a B particle at the rate k+(mu). In turn, any randomly moving B particle may spontaneously dissociate at the rate k-(lambda) into a geminate pair of As "born" at a distance lambda apart of each other. Within a formally exact approach based on Gardiner's Poisson representation method we show that the asymptotic t=infinity state attained by such diffusion-limited reactions is generally not a true thermodynamic equilibrium, but rather a nonequilibrium steady state, and that the law of mass action is invalid. The classical concepts hold only in case when the ratio k+(mu)k-(mu) does not depend on mu for any mu.

Saltatory drift in a randomly driven two-wave potential.

The dynamics of a classical particle in a one-dimensional, randomly driven potential is analysed both analytically and numerically. The potential considered here is composed of two identical spatially periodic saw-tooth-like components, one of which is externally driven by a random force. We show that under certain conditions the particle may travel against the averaged external force, performing a saltatory unidirectional drift with a constant velocity. Such a behaviour persists also in situations when the external force averages out to zero. We demonstrate that the physics behind this phenomenon stems from a particular behaviour of fluctuations in random force: upon reaching a certain level, random fluctuations exercise a locking function creating points of irreversibility which the particle cannot overpass. Repeated (randomly) in each cycle, this results in a saltatory unidirectional drift. This mechanism resembles the work of an escapement-type device in watches. Considering the overdamped limit, we propose simple analytical estimates for the particle's terminal velocity.

Exactly solvable model of monomer-monomer reactions on a two-dimensional random catalytic substrate.

We study the equilibrium properties of a monomer-monomer A+B--> reaction on a two-dimensional substrate containing randomly placed catalytic bonds. Interacting A and B species undergo continuous exchanges with particle reservoirs and react as soon as a pair of unlike particles appears on sites connected by a catalytic bond. For annealed disorder in the placement of catalytic bonds the model is mapped onto a general spin S=1 model and solved exactly for the pressure in a particular case. At equal activities of the two species a second order phase transition is revealed.

Lattice theory of trapping reactions with mobile species.

We present a stochastic lattice theory describing the kinetic behavior of trapping reactions A+B-->B, in which both the A and B particles perform an independent stochastic motion on a regular hypercubic lattice. Upon an encounter of an A particle with any of the B particles, A is annihilated with a finite probability; finite reaction rate is taken into account by introducing a set of two-state random variables--"gates," imposed on each B particle, such that an open (closed) gate corresponds to a reactive (passive) state. We evaluate here a formal expression describing the time evolution of the A particle survival probability, which generalizes our previous results. We prove that for quite a general class of random motion of the species involved in the reaction process, for infinite or finite number of traps, and for any time t, the A particle survival probability is always larger in the case when A stays immobile, than in situations when it moves.