Pressure-induced isostructural phase transition of metal-doped silicon clathrates

We propose an atomistic model for the pressure-induced isostructural phase transition of metal-doped silicon clathrates, Ba8Si46 and K8Si46, that has been observed at 14 GPa and 23 GPa, respectively. The model explains successfully the equation of state, transition pressure, change of Raman spectra and dependence on the doped cations as well as the effects of substituting Si(6c) atoms with noble metals.Comment: 5 pages, two coumn, 5 figures. See http://www.iitaka.org/down.html for more informatio

Benchmarking the performance of Density Functional Theory and Point Charge Force Fields in their Description of sI Methane Hydrate against Diffusion Monte Carlo

High quality reference data from diffusion Monte Carlo calculations are presented for bulk sI methane hydrate, a complex crystal exhibiting both hydrogen-bond and dispersion dominated interactions. The performance of some commonly used exchange-correlation functionals and all-atom point charge force fields is evaluated. Our results show that none of the exchange-correlation functionals tested are sufficient to describe both the energetics and the structure of methane hydrate accurately, whilst the point charge force fields perform badly in their description of the cohesive energy but fair well for the dissociation energetics. By comparing to ice Ih, we show that a good prediction of the volume and cohesive energies for the hydrate relies primarily on an accurate description of the hydrogen bonded water framework, but that to correctly predict stability of the hydrate with respect to dissociation to ice Ih and methane gas, accuracy in the water-methane interaction is also required. Our results highlight the difficulty that density functional theory faces in describing both the hydrogen bonded water framework and the dispersion bound methane.Comment: 8 pages, 4 figures, 1 table. Minor typos corrected and clarification added in Method

Kepone monitoring at Skiffs Creek : in fulfillment of contract number DACW65-79-C-0027

Kepone entered the James River estuary from point sources of production and through runoff from unauthorized disposal sites in the vicinity of Hopewell, Virginia. The total quantity of Kepone released to the river is not known, however, about 1.5 x 106 kg were produced between 1966 and 1975. At present we estimate that 30,000 kg reside in contaminated sediments of the estuary. Bed sediments are contaminated from the source at Hopewell to Hampton Roads, a distance of 88 kilometers. Patterns of contamination vary with sediment type and distance from the source. Major Kepone sinks exist in the Jamestown - Dancing Point reach and in Burwell Bay. Sediments from these zones are generally finer-grained and more enriched in organic matter than elsewhere and these zones are sites of relatively high sediment accumulation and fast deposition. This extensive contamination of the river sediments by Kepone presents problems for managers having to make decisions on dredging actions in the river. The most important questions which need to be answered concerning dredging activities are: 1) Will dredging result in significant quantities of Kepone being released to the environment? 2) Will the releases spread the contamination or result in increased bioaccumulation of Kepone in organisms? 3) Will the spoil disposal methods release Kepone to the marine environment or ground water? (...

Stability, Adsorption and Diffusion of CH4, CO2 and H2 in Clathrate Hydrates

We present a study of the adsorption and diffusion of CH4, CO2 and H2 molecules in clathrate hydrates using ab initio van der Waals density functional formalism [Dion et al. Phys. Rev. Lett. 92, 246401 (2004)]. We find that the adsorption energy is dominated by van der Waals interactions and that, without them, gas hydrates would not be stable. We calculate the maximum adsorption capacity as well as the maximum hydrocarbon size that can be adsorbed.The relaxation of the host lattice is essential for a good description of the diffusion activation energies, which are estimated to be of the order of 0.2, 0.4, and 1.0 eV for H2, CO2, and CH4, respectively.Comment: 4 pages, 4 figures, 3 table

On the thermodynamic stability and structural transition of clathrate hydrates

Gas mixtures of methane and ethane form structure II clathrate hydrates despite the fact that each of pure methane and pure ethane gases forms the structure I hydrate. Optimization of the interaction potential parameters for methane and ethane is attempted so as to reproduce the dissociation pressures of each simple hydrate containing either methane or ethane alone. An account for the structural transitions between type I and type II hydrates upon changing the mole fraction of the gas mixture is given on the basis of the van der Waals and Platteeuw theory with these optimized potentials. Cage occupancies of the two kinds of hydrates are also calculated as functions of the mole fraction at the dissociation pressure and at a fixed pressure well above the dissociation pressure

Artifacts at 4.5 and 8.0 um in Short Wavelength Spectra from the Infrared Space Observatory

Spectra from the Short Wavelength Spectrometer (SWS) on ISO exhibit artifacts at 4.5 and 8 um. These artifacts appear in spectra from a recent data release, OLP 10.0, as spurious broad emission features in the spectra of stars earlier than ~F0, such as alpha CMa. Comparison of absolutely calibrated spectra of standard stars to corresponding spectra from the SWS reveals that these artifacts result from an underestimation of the strength of the CO and SiO molecular bands in the spectra of sources used as calibrators by the SWS. Although OLP 10.0 was intended to be the final data release, these findings have led to an additional release addressing this issue, OLP 10.1, which corrects the artifacts.Comment: 14 pages, AASTex, including 5 figures. Accepted by ApJ Letter

Force and energy dissipation variations in non-contact atomic force spectroscopy on composite carbon nanotube systems

UHV dynamic force and energy dissipation spectroscopy in non-contact atomic force microscopy were used to probe specific interactions with composite systems formed by encapsulating inorganic compounds inside single-walled carbon nanotubes. It is found that forces due to nano-scale van der Waals interaction can be made to decrease by combining an Ag core and a carbon nanotube shell in the Ag@SWNT system. This specific behaviour was attributed to a significantly different effective dielectric function compared to the individual constituents, evaluated using a simple core-shell optical model. Energy dissipation measurements showed that by filling dissipation increases, explained here by softening of C-C bonds resulting in a more deformable nanotube cage. Thus, filled and unfilled nanotubes can be discriminated based on force and dissipation measurements. These findings have two different implications for potential applications: tuning the effective optical properties and tuning the interaction force for molecular absorption by appropriately choosing the filling with respect to the nanotube.Comment: 22 pages, 6 figure

The Nystrom plus Correction Method for Solving Bound State Equations in Momentum Space

A new method is presented for solving the momentum-space Schrodinger equation with a linear potential. The Lande-subtracted momentum space integral equation can be transformed into a matrix equation by the Nystrom method. The method produces only approximate eigenvalues in the cases of singular potentials such as the linear potential. The eigenvalues generated by the Nystrom method can be improved by calculating the numerical errors and adding the appropriate corrections. The end results are more accurate eigenvalues than those generated by the basis function method. The method is also shown to work for a relativistic equation such as the Thompson equation.Comment: Revtex, 21 pages, 4 tables, to be published in Physical Review

First principles molecular dynamics study of filled ice hydrogen hydrate

We investigated structural changes, phase diagram, and vibrational properties of hydrogen hydrate in filled-ice phase C2 by using first principles molecular dynamics simulation. It was found that the experimentally reported 'cubic' structure is unstable at low temperature and/or high pressure. The 'cubic' structure reflects the symmetry at high (room) temperature where the hydrogen bond network is disordered and the hydrogen molecules are orientationally disordered due to thermal rotation. In this sense, the 'cubic' symmetry would definitely be lowered at low temperature where the hydrogen bond network and the hydrogen molecules are expected to be ordered. At room temperature and below 30 GPa, it is the thermal effects that play an essential role in stabilizing the structure in 'cubic' symmetry. Above 60 GPa, the hydrogen bonds in the framework would be symmetrized and the hydrogen bond order-disorder transition would disappear. These results also suggest the phase behavior of other filled-ice hydrates. In the case of rare gas hydrate, there would be no guest molecues rotation-nonrotation transition since the guest molecules keep their spherical symmetry at any temperature. On the contrary methane hydrate MH-III would show complex transitions due to the lower symmetry of the guest molecule. These results would encourage further experimental studies, especially NMR spectroscopy and neutron scattering, on the phases of filled-ice hydrates at high pressures and/or low temperatures.Comment: typos correcte