Lattice-gas Monte Carlo study of adsorption in pores

A lattice gas model of adsorption inside cylindrical pores is evaluated with Monte Carlo simulations. The model incorporates two kinds of site: (a line of) ``axial'' sites and surrounding ``cylindrical shell'' sites, in ratio 1:7. The adsorption isotherms are calculated in either the grand canonical or canonical ensembles. At low temperature, there occur quasi-transitions that would be genuine thermodynamic transitions in mean-field theory. Comparison between the exact and mean-field theory results for the heat capacity and adsorption isotherms are provided

Adsorption of Xe and Ar on Quasicrystalline Al-Ni-Co

An interaction potential energy between and adsorbate (Xe and Ar) and the 10-fold Al-Ni-Co quasicrystal is computed by summing over all adsorbate-substrate interatomic interactions. The quasicrystal atoms' coordinates are obtained from LEED experiments and the Lennard-Jones parameters of Xe-Al, Xe-Ni and Xe-Co are found using semiempirical combining rules. The resulting potential energy function of position is highly corrugated. Monolayer adsorption of Xe and Ar on the quasicrystal surface is investigated in two cases: 1) in the limit of low coverage (Henry's law regime), and 2) at somewhat larger coverage, when interactions between adatoms are considered through the second virial coefficient, C_{AAS}. A comparison with adsorption on a flat surface indicates that the corrugation enhances the effect on Xe-Xe (Ar-Ar) interactions. The theoretical results for the low coverage adsorption regime are compared to experimental (LEED isobar) data.Comment: 12 pages, 8figure

Phase transitions and ordering of confined dipolar fluids

We apply a modified mean-field density functional theory to determine the phase behavior of Stockmayer fluids in slitlike pores formed by two walls with identical substrate potentials. Based on the Carnahan-Starling equation of state, a fundamental-measure theory is employed to incorporate the effects of short-ranged hard sphere - like correlations while the long-ranged contributions to the fluid interaction potential are treated perturbatively. The liquid-vapor, ferromagnetic liquid - vapor, and ferromagnetic liquid - isotropic liquid first-order phase separations are investigated. The local orientational structure of the anisotropic and inhomogeneous ferromagnetic liquid phase is also studied. We discuss how the phase diagrams are shifted and distorted upon varying the pore width.Comment: 15 pages including 8 figure

Noble gas films on a decagonal AlNiCo quasicrystal

Thermodynamic properties of Ne, Ar, Kr, and Xe adsorbed on an Al-Ni-Co quasicrystalline surface (QC) are studied with Grand Canonical Monte Carlo by employing Lennard-Jones interactions with parameter values derived from experiments and traditional combining rules. In all the gas/QC systems, a layer-by-layer film growth is observed at low temperature. The monolayers have regular epitaxial fivefold arrangements which evolve toward sixfold close-packed structures as the pressure is increased. The final states can contain either considerable or negligible amounts of defects. In the latter case, there occurs a structural transition from five to sixfold symmetry which can be described by introducing an order parameter, whose evolution characterizes the transition to be continuous or discontinuous as in the case of Xe/QC (first-order transition with associated latent heat). By simulating fictitious noble gases, we find that the existence of the transition is correlated with the size mismatch between adsorbate and substrate's characteristic lengths. A simple rule is proposed to predict the phenomenon.Comment: 19 pages. 8 figures. (color figures can be seen at http://alpha.mems.duke.edu/wahyu/ or http://www.iop.org/EJ/abstract/0953-8984/19/1/016007/

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

Systematic model behavior of adsorption on flat surfaces

A low density film on a flat surface is described by an expansion involving the first four virial coefficients. The first coefficient (alone) yields the Henry's law regime, while the next three correct for the effects of interactions. The results permit exploration of the idea of universal adsorption behavior, which is compared with experimental data for a number of systems

Isotopic and spin selectivity of H_2 adsorbed in bundles of carbon nanotubes

Due to its large surface area and strongly attractive potential, a bundle of carbon nanotubes is an ideal substrate material for gas storage. In addition, adsorption in nanotubes can be exploited in order to separate the components of a mixture. In this paper, we investigate the preferential adsorption of D_2 versus H_2(isotope selectivity) and of ortho versus para(spin selectivity) molecules confined in the one-dimensional grooves and interstitial channels of carbon nanotube bundles. We perform selectivity calculations in the low coverage regime, neglecting interactions between adsorbate molecules. We find substantial spin selectivity for a range of temperatures up to 100 K, and even greater isotope selectivity for an extended range of temperatures,up to 300 K. This isotope selectivity is consistent with recent experimental data, which exhibit a large difference between the isosteric heats of D_2 and H_2 adsorbed in these bundles.Comment: Paper submitted to Phys.Rev. B; 17 pages, 2 tables, 6 figure