Search

The discovery of fullerenes has stimulated extensive exploration of the resulting behavior of adsorbed films. Our study addresses the planar substrates graphene-fluoride (GF) and graphane (GH) in comparison to graphene. We present initial results concerning the potential energy, energy bands and low density behavior of 4He and 3He films on such different surfaces. For example, while graphene presents an adsorption potential that is qualitatively similar to that on graphite, GF and GH yield potentials with different symmetry, a number of adsorption sites double that on graphene/graphite and a larger corrugation for the adatom. In the case of GF, the lowest energy band width is similar to that on graphite but the He atom has a significantly larger effective mass and the adsorption energy is about three time that on graphite. Implications concerning the monolayer phase diagram of 4He are explored with the exact path integral ground state method. A commensurate ordered state similar to the sqrt{3} x sqrt{3} R30^o state on graphite is found the be unstable both on GF and on GH. The ground states of submonolayer 4He on both GF and GH are superfluids with a Bose Einstein condensate fraction of about 10%., Comment: 6 pages, 3 figures, LT26 proceedings, accepted for publication in Journal of Physics: Conference Series

This paper reviews recent progress in the study of rare gas films on quasicrystalline surfaces. The adsorption of Xe on the 10-fold surface of decagonal Al-Ni-Co was studied using low-energy electron diffraction (LEED). The results of these studies prompted the development of a theoretical model, which successfully reproduced the thermodynamic parameters found in the experiment. Grand canonical Monte Carlo (GCMC) simulations for Xe produced structures agreed with the experimental observations of the adsorption structures and provided a deeper insight into the nature of the ordering. A first-order commensurate-incommensurate transition that involves a transition from a quasicrystalline five-fold stucture to a periodic hexagonal structure was discovered and characterized for the Xe monolayer. The five rotational domains of the hexagonal structure observed in the LEED study were shown in the GCMC study to be mediated by pentagonal defects that are entropic in nature, and not by substrate defects. The GCMC study found an absence of any such transition for Kr, Ar and Ne on the same surface. A detailed analysis of this transition led to the conclusion that the formation of the hexagonal layer depends on matching the gas and substrate characteristic lengths., Comment: 9 pages, 3 figures, 3 tables, to appear in Philos. Mag. (2006)

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/)

Helium atoms and hydrogen molecules can be strongly bound inside interstitial channels within bundles of carbon nanotubes. An exploration of the low energy and low temperature properties of He-3 atoms is presented here. Recent study of the analogous He-4 system has shown that the effect of heterogeneity is to yield a density of states N(E) that is qualitatively different from the one-dimensional (1D) form of N(E) that would occur for an ideal set of identical channels. In particular, the functional form of N(E) is that of a 4D gas near the very lowest energies and a 2D gas at somewhat higher energies. Similar behavior is found here for He-3. The resulting thermodynamic behavior of this fermi system is computed, yielding an anomalous form of the heat capacity and its dependence on coverage., Comment: 11 pages, 6 figures

A wetting transition occurs when the contact angle of a liquid drop on a surface changes from a nonzero value to zero. Such a transition has never been observed for water on any solid surface. This paper discusses the value of the temperature T_w at which the transition should occur for water on graphite. A simple model, previously used for nonpolar fluids, predicts the value of $T_w$ as a function of the well-depth D of the adsorption potential. While $D$ is not well known for the case of water/graphite, the model implies that T_w is likely to fall in the range 350 to 500 K. Experimental search for this transition is warranted. Water wetting transition temperatures on other surfaces are also discussed., Comment: 14 pages, 2 figures

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, 8figures

Helium atoms or hydrogen molecules are believed to be strongly bound within the interstitial channels (between three carbon nanotubes) within a bundle of many nanotubes. The effects on adsorption of a nonuniform distribution of tubes are evaluated. The energy of a single particle state is the sum of a discrete transverse energy Et (that depends on the radii of neighboring tubes) and a quasicontinuous energy Ez of relatively free motion parallel to the axis of the tubes. At low temperature, the particles occupy the lowest energy states, the focus of this study. The transverse energy attains a global minimum value (Et=Emin) for radii near Rmin=9.95 Ang. for H2 and 8.48 Ang.for He-4. The density of states N(E) near the lowest energy is found to vary linearly above this threshold value, i.e. N(E) is proportional to (E-Emin). As a result, there occurs a Bose-Einstein condensation of the molecules into the channel with the lowest transverse energy. The transition is characterized approximately as that of a four dimensional gas, neglecting the interactions between the adsorbed particles. The phenomenon is observable, in principle, from a singular heat capacity. The existence of this transition depends on the sample having a relatively broad distribution of radii values that include some near Rmin., Comment: 21 pages, 9 figures

The study of particle motion on spherical surfaces is relevant to adsorption on buckyballs and other solid particles. This paper reports results for the binding energy of such dimers, consisting of two light particles (He atoms or hydrogen molecules) constrained to move on a spherical surface. The binding energy reaches a particularly large value when the radius of the sphere is about 3/4 of the particles' diameter., Comment: 6 pages, 3 figures, submitted to JLTP, conference proceedings QFS 2003

We examine the hydrodynamic phonon spectrum of a monolayer film adsorbed on the wall of a spherical pore. Due to the boundary conditions, the monolayer film exhibits a discrete phonon spectrum. The corresponding density of states per unit frequency is thus a set of delta functions and the heat capacity exhibits Arrhenius behavior at low temperatures. At high temperatures, the heat capacity approaches the C ~ T^2 behavior of a two-dimensional monolayer film. Our results for the spherical surface film are compared to previous calculations for films confined to a cylindrical surface.

In some respects, a cluster consisting of many atoms may be regarded as a single large atom. Knowing the dielectric properties of such a cluster permits one to evaluate the form of the van der Waals (dispersion) interactions between two clusters or between one cluster and a surface. In this paper, we derive these interactions in two extreme opposite regimes of separation: fully retarded and nonretarded. In the fully retarded regime (very large separation), the magnitude of the interaction is determined by just the static polarizability of the cluster(s). In the nonretarded regime (small separation), we employ a single resonant frequency model of thecluster polarizability to derive expressions for the interactions' coefficients. Numerical examples are presented to demonstrate that many-body screening of these interactions can be significant. The results represent the corrections to the commonly used approximation of pairwise additivity of interatomic interactions.

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 figures

We evaluate, by means of variational calculations, the bound state energy E_B of a pair of charges located on the surface of a cylinder, interacting via Coulomb potential - e^2 / r . The trial wave function involves three variational parameters. E_B is obtained as a function of the reduced curvature C = a_0 / R, where a_0 is the Bohr radius and R is the radius of the cylinder. We find that the energetics of binding exhibits a monotonic trend as a function of C ; the known 1D and 2D limits of E_B are reproduced accurately by our calculation. E_B is relatively insensitive to curvature for small C . Its value is ~ 1% higher at C = 1 than at C = 0. This weak dependence is confirmed by a perturbation theory calculation. The high curvature regime approximates the 1D Coulomb model; within our variational approach, E_B has a logarithmic divergence as R approaches zero. The proposed variational method is applied to the case of donors in single-wall carbon nanotubes (SWCNTs)., Comment: 9 pages, 4 figures, paper submitted to PRB

We employ a simple model to describe the phase behavior of 4He and Ar in a hypothetical porous material consisting of a regular array of infinitely long, solid, parallel cylinders. We find that high porosity geometries exhibit two transitions: from vapor to film and from film to capillary condensed liquid. At low porosity, the film is replaced by a ``necking'' configuration, and for a range of intermediate porosity there are three transitions: from vapor to film, from film to necking and from necking to a capillary condensed phase., Comment: 14 pages, 7 figures

We evaluate the cohesive energies E$_b$ of four systems in which particles move on a cylindrical surface, at fixed distance R from the axis. We find quite nonuniversal dependences of E$_b$ on R. For the Coulomb binding problem, E$_b$ is a monotonically decreasing function of R. For three problems involving Lennard-Jones interactions, the behavior is nonmonotonic; E$_b$ is larger at R = $\infty$ than at R=0; the maximum binding corresponds to R $\sim 0.7 \sigma$ (the hard core parameter). Consequences of the enhanced binding are discussed., Comment: 9 pages,5 figures, submitted to PRL

A theoretical study on the rotational dynamics of H2 molecules trapped in the interstitial channels (ICs) of a carbon nanotube bundle is presented. The potential used in this study is modeled as a sum of atom-atom (C-H) van der Waals interactions and electrostatic interactions of the molecule with the surrounding nanotubes.The rotational energy spectra is calculated using a product wave function, where the coupling between translational and rotational modes is treated in a mean-field manner . Molecular dynamics (MD) simulation study was performed for estimating the hydrogen rotational barrier. Both theoretical calculations and simulation results reveal the existence of a large rotational barrier (~ 40 meV). The consequences of this rotational barrier for the rotational energy levels are worked out in detail., Comment: 21 pages, 3 figures, 1 table, accepted for publication in the Journal of Chemical Physics

We explore the behavior of neon, xenon, and methane filmas adsorbed on the external surface of a bundle of carbon nanotubes. The methods used are classical: a ground state calculation, by grand potential energy minimization, and the grand canonical Monte Carlo (GCMC) method of simulation. Our results are similar to those found recently in a GCMC study of Ar and Kr. At low chemical potential (pressure) the particles form a quasi-one dimensional phase within the groove formed by two contiguous tubes. At higher chemical potential, there occurs a "three-stripe" phase aligned parallel to the groove (except for xenon). This is followed by monolayer and bilayer phases. The low temperature monolayer phase is striped; the number of stripes per nanotube is a quantized function of the adatom size. In the neon case, the bilayer regime also includes a second layer groove phase. Our results are compared with recent thermal and diffraction experiments. We find no evidence of a zig-zag phase reported recently.

We study the low temperature phase behavior of hydrogen within a bundle of carbon nanotubes. Because the carbon environment weakens the attraction between molecules within the same interstitial channel (IC), the ground state of the one-dimensional (1D) system is an uncondensed gas. When the screened attractive interaction between molecules in adjacent ICs is taken into account, the hydrogen ground state is a quasi-1D liquid. The critical temperature of this system is estimated., Comment: 4 pages, 4 figures

Grand canonical Monte Carlo simulations have been performed to determine the adsorption behavior of Ar and Kr atoms on the exterior surface of a rope (bundle) consisting of many carbon nanotubes. The computed adsorption isotherms reveal phase transitions associated with the successive creation of quasi-one dimensional lines of atoms near and parallel to the intersection of two adjacent nanotubes., Comment: 12 pages, 6 figures, submitted to J. Chem. Phys

We explore the equations of state and other properties of various quantum fluids (3He, 4He, their mixtures, and H_2) confined within individual carbon nanotubes. Above a threshold number of particles, N_a, the fluid density near the axis begins to grow above a negligibly small value. The properties of this axial fluid phase are sensitive to the tube size and hence to the transverse compression in the case of a bundle of nanotubes. We consider He at zero temperature and H_2 at low temperatures., Comment: 19 pages, 17 figures, submitted to J. Low Temp. Phys

Model calculations are presented which predict whether or not an arbitrary gas experiences significant absorption within carbon nanotubes and/or bundles of nanotubes. The potentials used in these calculations assume a conventional form, based on a sum of two-body interactions with individual carbon atoms; the latter employ energy and distance parameters which are derived from empirical combining rules. The results confirm intuitive expectation that small atoms and molecules are absorbed within both the interstitial channels and the tubes, while large atoms and molecules are absorbed almost exclusively within the tubes., Comment: 9 pages, 12 figures, submitted to PRB Newer version (8MAR2K). There was an error in the old one (23JAN2K). Please download this

The wetting of solid surfaces by fluids is a problem of great practical importance that has been extensively studied over the years. Most often, the experimental work has involved measurements of the contact angle made by a liquid on the solid surface of interest. Young's equation gives the relation between the contact angle and the interfacial tensions. An alternative to the contact angle computation is the more generally applicable formulation of this problem based on simulations (and measurements) of adsorption isotherms for a fluid on a weakly interacting solid surface. We present some GCMC computations for the case of heterogeneous surfaces., Comment: 7 pages, 7 figures

Helium atoms are strongly attracted to the interstitial channels within a bundle of carbon nanotubes. The strong corrugation of the axial potential within a channel can produce a lattice gas system where the weak mutual attraction between atoms in neighboring channels of a bundle induces condensation into a remarkably anisotropic phase with very low binding energy. We estimate the binding energy and critical temperature for 4He in this novel quasi-one-dimensional condensed state. At low temperatures, the specific heat of the adsorbate phase (fewer than 2% of the total number of atoms) greatly exceeds that of the host material., Comment: 8 pages, 3 figures, submitted to PRL (corrected typo in abstract)

Grand canonical simulations are used to calculate adsorption isotherms of various classical gases on alkali metal and Mg surfaces. Ab initio adsorption potentials and Lennard-Jones gas-gas interactions are used. Depending on the system, the resulting behavior can be nonwetting for all temperatures studied, complete wetting, or (in the intermediate case) exhibit a wetting transition. An unusual variety of wetting transitions at the triple point is found in the case of a specific adsorption potential of intermediate strength. The general threshold for wetting near the triple point is found to be close to that predicted with a heuristic model of Cheng et al. This same conclusion was drawn in a recent experimental and simulation study of Ar on CO_2 by Mistura et al. These results imply that a dimensionless wetting parameter w is useful for predicting whether wetting behavior is present at and above the triple temperature. The nonwetting/wetting crossover value found here is w circa 3.3., Comment: 15 pages, 8 figures

We use the grand canonical Monte Carlo method to study the nature of wetting transitions on a variety of heterogeneous surfaces. The model system we explore, Ne adsorption on Mg, is one for which a prewetting transition has been found in our previous simulations. We find that the first order transition present on the flat surface is absent from the rough surface. Nevertheless, the resulting isotherms are, in some cases, so close to being discontinuous that the distinction would be difficult to discern in most experiments., Comment: 14 pages, 9 draft figures, submitted to Physical Review E. Original figures (bw and color) in http://pcinfm1.pd.infn.it/~auro/papers/9808299.zip

We explore the properties of atoms confined to the interstitial regions within a carbon nanotube bundle. We find that He and Ne atoms are of ideal size for physisorption interactions, so that their binding energies are much greater there than on planar surfaces of any known material. Hence high density phases exist at even small vapor pressure. There can result extraordinary anisotropic liquids or crystalline phases, depending on the magnitude of the corrugation within the interstitial channels., Comment: 6 pages, 4 figures, to be published in J. Low Temp. Phys

We report studies of the wetting behavior of Ne on very weakly attractive surfaces, carried out with the Grand Canonical Monte Carlo method. The Ne-Ne interaction was taken to be of Lennard-Jones form, while the Ne-surface interaction was derived from an ab initio calculation of Chizmeshya et al. Nonwetting behavior was found for Li, Rb, and Cs in the temperature regime explored (i.e., T < 42 K). Drying behavior was manifested in a depleted fluid density near the Cs surface. In contrast, for the case of Mg (a more attractive potential) a prewetting transition was found near T= 28 K. This temperature was found to shift slightly when a corrugated potential was used instead of a uniform potential. The isotherm shape and the density profiles did not differ qualitatively between these cases., Comment: 22 pages, 12 figures, submitted to Phys. Rev. E