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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 its 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., Comment: 18 pages, 4 figures, J. Chem. Phys. (in print; full bibliographic info and DOI to be added once available)

We study the effect of spatial confinement on the strength of propulsive diffusiophoretic forces acting on a particle that generates density gradients by exploiting the chemical free energy of its environment. Using a recently proposed simple model of a self-propelling device driven by chemical reactions taking place on some parts of its surface, we demonstrate that the force significantly increases in the presence of confining walls. We also show that such effects become even more pronounced in two-dimensional systems., Comment: 6 pages, 2 figures, uses epl2.cls

We study the equilibrium properties of a model for a binary mixture of catalytically-reactive monomers adsorbed on a two-dimensional substrate decorated by randomly placed catalytic bonds. The interacting $A$ and $B$ monomer species undergo continuous exchanges with particle reservoirs and react ($A + B \to \emptyset$) as soon as a pair of unlike particles appears on sites connected by a catalytic bond. For the case of annealed disorder in the placement of the catalytic bonds this model can be mapped onto a classical spin model with spin values $S = -1,0,+1$, with effective couplings dependent on the temperature and on the mean density $q$ of catalytic bonds. This allows us to exploit the mean-field theory developed for the latter to determine the phase diagram as a function of $q$ in the (symmetric) case in which the chemical potentials of the particle reservoirs, as well as the $A-A$ and $B-B$ interactions are equal., Comment: 12 pages, 4 figures

The use of ultra-thin, i.e., monolayer films plays an important role for the emerging field of nano-fluidics. Since the dynamics of such films is governed by the interplay between substrate-fluid and fluid-fluid interactions, the transport of matter in nanoscale devices may be eventually efficiently controlled by substrate engineering. For such films, the dynamics is expected to be captured by two-dimensional lattice-gas models with interacting particles. Using a lattice gas model and the non-linear diffusion equation derived from the microscopic dynamics in the continuum limit, we study two problems of relevance in the context of nano-fluidics. The first one is the case in which along the spreading direction of a monolayer a mesoscopic-sized obstacle is present, with a particular focus on the relaxation of the fluid density profile upon encountering and passing the obstacle. The second one is the mixing of two monolayers of different particle species which spread side by side following the merger of two chemical lanes, here defined as domains of high affinity for fluid adsorption surrounded by domains of low affinity for fluid adsorption., Comment: 12 pages, 3 figures

We overview recent results on intrinsic frictional properties of adsorbed monolayers, composed of mobile hard-core particles undergoing continuous exchanges with a vapor phase. In terms of a dynamical master equation approach we determine the velocity of a biased impure molecule - the tracer particle (TP), constrained to move inside the adsorbed monolayer probing its frictional properties, define the frictional forces exerted by the monolayer on the TP, as well as the particles density distribution in the monolayer., Comment: 12 pages, 5 figures, talk at the MRS Fall 2003 Meeting, Boston, December 1-5, 2003

We present an \textit{exactly solvable} model of a monomer-monomer $A + B \to \emptyset$ reaction on a 2D inhomogeneous, catalytic substrate and study the equilibrium properties of the two-species adsorbate. The substrate contains randomly placed catalytic bonds of mean density $q$ which connect neighboring adsorption sites. The interacting $A$ and $B$ (monomer) species undergo continuous exchanges with corresponding adjacent gaseous reservoirs. A reaction $A + B \to \emptyset$ takes place instantaneously if $A$ and $B$ particles occupy adsorption sites connected by a catalytic bond. We find that for the case of \textit{annealed} disorder in the placement of the catalytic bonds the reaction model under study can be mapped onto the general spin $S = 1$ (GS1) model. Here we concentrate on a particular case in which the model reduces to an exactly solvable Blume-Emery-Griffiths (BEG) model (T. Horiguchi, Phys. Lett. A {\bf 113}, 425 (1986); F.Y. Wu, Phys. Lett. A, {\bf 116}, 245 (1986)) and derive an exact expression for the disorder-averaged equilibrium pressure of the two-species adsorbate. We show that at equal partial vapor pressures of the $A$ and $B$ species this system exhibits a second-order phase transition which reflects a spontaneous symmetry breaking with large fluctuations and progressive coverage of the entire substrate by either one of the species., Comment: 4 pages, 2 figures, submitted to Phys. Rev. Lett

We study the spreading kinetics of a monolayer of hard-core particles on a semi-infinite, chemically heterogeneous solid substrate, one side of which is coupled to a particle reservoir. The substrate is modeled as a square lattice containing two types of sites -- ordinary ones and special, chemically active sites placed at random positions with mean concentration $\alpha$. These special sites temporarily immobilize particles of the monolayer which then serve as impenetrable obstacles for the other particles. In terms of a mean-field-type theory, we show that the mean displacement $X_0(t)$ of the monolayer edge grows with time $t$ as $X_0(t) = \sqrt{2 D_{\alpha} t \ln(4 D_{\alpha} t/\pi a^2)}$, ($a$ being the lattice spacing). This time dependence is confirmed by numerical simulations; $D_{\alpha}$ is obtained numerically for a wide range of values of the parameter $\alpha$ and trapping times of the chemically active sites. We also study numerically the behavior of a stationary particle current in finite samples. The question of the influence of attractive particle-particle interactions on the spreading kinetics is also addressed., Comment: Latex, 27 pages, 7 figures, to appear in Coll. Surf. A

In a series of recent papers van Gastel et al have presented first experimental evidence that impure, Indium atoms, embedded into the first layer of a Cu(001) surface, are not localized within the close-packed surface layers but make concerted, long excursions visualized in a series of STM images. Such excursions occur due to continuous reshuffling of the surface following the position exchanges of both impure and host atoms with the naturally occuring surface vacancies. Van Gastel et al have also formulated an original lattice-gas type model with asymmetric exchange probabilities, whose numerical solution is in a good agreement with the experimental data. In this paper we propose an exact lattice solution of several versions of this model., Comment: Latex, 4 pages, 2 figures, to appear in Phys. Rev. E (RC)

We study propagation dynamics of a particle phase in a single-file pore connected to a reservoir of particles (bulk liquid phase). We show that the total mass $M(t)$ of particles entering the pore up to time $t$ grows as $M(t) = 2 m(J,\rho_F) \sqrt{D_0 t}$, where $D_0$ is the "bare" diffusion coefficient and the prefactor $m(J,\rho_F)$ is a non-trivial function of the reservoir density $\rho_F$ and the amplitude $J$ of attractive particle-particle interactions. Behavior of the dynamic density profiles is also discussed., Comment: Latex, 12 pages, to appear in the Proceedings of the MRS Fall 2000 Meeting

We study analytically kinetics of an elementary bimolecular reaction scheme of the Langmuir-Hinshelwood type taking place on a d-dimensional catalytic substrate. We propose a general approach which takes into account explicitly the influence of spatial correlations on the time evolution of particles mean densities and allows for the analytical analysis. In terms of this approach we recover some of known results concerning the time evolution of particles mean densities and establish several new ones., Comment: Latex, 25 pages, one figure, submitted to J. Chem. Phys

We study the time evolution of a sessile liquid droplet, which is initially put onto a solid surface in a non-equilibrium configuration and then evolves towards its equilibrium shape. We adapt here the standard approach to the dynamics of mechanical dissipative systems, in which the driving force, i.e. the gradient of the system's Lagrangian function, is balanced against the rate of the dissipation function. In our case the driving force is the loss of the droplet's free energy due to the increase of its base radius, while the dissipation occurs due to viscous flows in the core of the droplet and due to frictional processes in the vicinity of the advancing contact line, associated with attachment of fluid particles to solid. Within this approach we derive closed-form equations for the evolution of the droplet's base radius, and specify several regimes at which different dissipation channels dominate. Our analytical predictions compare very well with experimental data., Comment: Latex, 15 pages, 5 figures and 1 table, to appear in Langmuir

We consider dynamics of an isolated polymer chain with a chemically active end-bead on a 2D solid substrate containing immobile, randomly placed chemically active sites (traps). For a particular situation when the end-bead can be irreversibly trapped by any of these sites, which results in a complete anchoring of the whole chain, we calculate the time evolution of the probability $P_{ch}(t)$ that the initially non-anchored chain remains mobile until time $t$. We find that for relatively short chains $P_{ch}(t)$ follows at intermediate times a standard-form 2D Smoluchowski-type decay law $ln P_{ch}(t) \sim - t/ln(t)$, which crosses over at very large times to the fluctuation-induced dependence $ln P_{ch}(t) \sim - t^{1/2}$, associated with fluctuations in the spatial distribution of traps. We show next that for long chains the kinetic behavior is quite different; here the intermediate-time decay is of the form $ln P_{ch}(t) \sim - t^{1/2}$, which is the Smoluchowski-type law associated with subdiffusive motion of the end-bead, while the long-time fluctuation-induced decay is described by the dependence $ln P_{ch}(t) \sim - t^{1/4}$, stemming out of the interplay between fluctuations in traps distribution and internal relaxations of the chain., Comment: Latex file, 19 pages, one ps figure, to appear in PRE

We study the behavior of a semi-infinite monolayer, which is placed initially on a half of an infinite in both directions, ideal crystalline surface, and then evolves in time due to random motion of the monolayer particles. Particles dynamics is modeled as the Kawasaki particle-vacancy exchange process in the presence of long-range attractive particle-particle interactions. In terms of an analytically solvable mean-field-type approximation we calculate the mean displacement X(t) of the monolayer edge and discuss the conditions under which such a monolayer spreads (X(t) > 0), partially wets (X(t) = 0) or dewets from the solid surface (X(t) < 0)., Comment: 4 pages, 2 figures, to appear in PRE (RC)

We study experimentally the molecular weight $M$ dependence of spreading rates of molecularly thin precursor films, growing at the bottom of droplets of polymer liquids. In accord with previous observations, we find that the radial extension R(t) of the film grows with time as R(t) = (D_{exp} t)^{1/2}. Our data substantiate the M-dependence of D_{exp}; we show that it follows D_{exp} \sim M^{-\gamma}, where the exponent \gamma is dependent on the chemical composition of the solid surface, determining its frictional properties with respect to the molecular transport. In the specific case of hydrophilic substrates, the frictional properties can be modified by the change of the relative humidity (RH). We find that \gamma \approx 1 at low RH and tends to zero when RH gets progressively increased. We propose simple theoretical arguments which explain the observed behavior in the limits of low and high RH., Comment: 4 pages, 2 figures, to appear in PRL

We study the behavior of a monolayer, which occupies initially a bounded region on an ideal crystalline surface and then evolves in time due to random hopping motion of the monolayer particles. In the case when the initially occupied region is the half-plane $X \leq 0$, we determine explicitly, in terms of an analytically solvable mean-field-type approximation, the mean displacement $X(t)$ of the monolayer edge. We find that $X(t) \approx A \sqrt{D_{0} t}$, in which law $D_{0}$ denotes the bare diffusion coefficient and the prefactor $A$ is a function of the temperature and of the particle-particle interactions parameters. We show that $A$ can be greater, equal or less than zero, and specify the critical parameter which distinguishes between the regimes of spreading ($A > 0)$, partial wetting ($A = 0$) and dewetting ($A < 0$)., Comment: 19 pages, 4 figures, to appear in J. of Mol. Liquids