Adsorption hysteresis and capillary condensation in disordered porous solids: a density functional study

We present a theoretical study of capillary condensation of fluids adsorbed in mesoporous disordered media. Combining mean-field density functional theory with a coarse-grained description in terms of a lattice-gas model allows us to investigate both the out-of-equilibrium (hysteresis) and the equilibrium behavior. We show that the main features of capillary condensation in disordered solids result from the appearance of a complex free-energy landscape with a large number of metastable states. We detail the numerical procedures for finding these states, and the presence or absence of transitions in the thermodynamic limit is determined by careful finite-size studies.Comment: 30 pages, 18 figures. To appear in J. Phys.: Condens. Matte

Capillary condensation in disordered porous materials: hysteresis versus equilibrium behavior

We study the interplay between hysteresis and equilibrium behavior in capillary condensation of fluids in mesoporous disordered materials via a mean-field density functional theory of a disordered lattice-gas model. The approach reproduces all major features observed experimentally. We show that the simple van der Waals picture of metastability fails due to the appearance of a complex free-energy landscape with a large number of metastable states. In particular, hysteresis can occur both with and without an underlying equilibrium transition, thermodynamic consistency is not satisfied along the hysteresis loop, and out-of-equilibrium phase transitions are possible.Comment: 4 pages, 4 figure

Slow dynamics of a confined supercooled binary mixture II: Q space analysis

We report the analysis in the wavevector space of the density correlator of a Lennard Jones binary mixture confined in a disordered matrix of soft spheres upon supercooling. In spite of the strong confining medium the behavior of the mixture is consistent with the Mode Coupling Theory predictions for bulk supercooled liquids. The relaxation times extracted from the fit of the density correlator to the stretched exponential function follow a unique power law behavior as a function of wavevector and temperature. The von Schweidler scaling properties are valid for an extended wavevector range around the peak of the structure factor. The parameters extracted in the present work are compared with the bulk values obtained in literature.Comment: 8 pages with 8 figures. RevTeX. Accepted for publication in Phys. Rev.

Lattice model of gas condensation within nanopores

We explore the thermodynamic behavior of gases adsorbed within a nanopore. The theoretical description employs a simple lattice gas model, with two species of site, expected to describe various regimes of adsorption and condensation behavior. The model includes four hypothetical phases: a cylindrical shell phase (S), in which the sites close to the cylindrical wall are occupied, an axial phase (A), in which sites along the cylinder's axis are occupied, a full phase (F), in which all sites are occupied, and an empty phase (E). We obtain exact results at T=0 for the phase behavior, which is a function of the interactions present in any specific problem. We obtain the corresponding results at finite T from mean field theory. Finally, we examine the model's predicted phase behavior of some real gases adsorbed in nanopores

Unified analysis of terminal-time control in classical and quantum systems

Many phenomena in physics, chemistry, and biology involve seeking an optimal control to maximize an objective for a classical or quantum system which is open and interacting with its environment. The complexity of finding an optimal control for maximizing an objective is strongly affected by the possible existence of sub-optimal maxima. Within a unified framework under specified conditions, control objectives for maximizing at a terminal time physical observables of open classical and quantum systems are shown to be inherently free of sub-optimal maxima. This attractive feature is of central importance for enabling the discovery of controls in a seamless fashion in a wide range of phenomena transcending the quantum and classical regimes.Comment: 10 page

Probing helium interfaces with light scattering : from fluid mechanics to statistical physics

We have investigated the formation of helium droplets in two physical situations. In the first one, droplets are atomised from superfluid or normal liquid by a fast helium vapour flow. In the second, droplets of normal liquid are formed inside porous glasses during the process of helium condensation. The context, aims, and results of these experiments are reviewed, with focus on the specificity of light scattering by helium. In particular, we discuss how, for different reasons, the closeness to unity of the index of refraction of helium allows in both cases to minimise the problem of multiple scattering and obtain results which it would not be possible to get using other fluids.Comment: 21 page