A Density Functional Study of Atomic Hydrogen and Oxygen Chemisorption on the Relaxed (0001) Surface of Double Hexagonal Close Packed Americium

Ab initio total energy calculations within the framework of density functional theory have been performed for atomic hydrogen and oxygen chemisorption on the (0001) surface of double hexagonal packed americium using a full-potential all-electron linearized augmented plane wave plus local orbitals method. Chemisorption energies were optimized with respect to the distance of the adatom from the relaxed surface for three adsorption sites, namely top, bridge, and hollow hcp sites, the adlayer structure corresponding to coverage of a 0.25 monolayer in all cases. Chemisorption energies were computed at the scalar-relativistic level (no spin-orbit coupling NSOC) and at the fully relativistic level (with spin-orbit coupling SOC). The two-fold bridge adsorption site was found to be the most stable site for O at both the NSOC and SOC theoretical levels with chemisorption energies of 8.204 eV and 8.368 eV respectively, while the three-fold hollow hcp adsorption site was found to be the most stable site for H with chemisorption energies of 3.136 eV at the NSOC level and 3.217 eV at the SOC level. The respective distances of the H and O adatoms from the surface were found to be 1.196 Ang. and 1.164 Ang. Overall our calculations indicate that chemisorption energies in cases with SOC are slightly more stable than the cases with NSOC in the 0.049-0.238 eV range. The work functions and net magnetic moments respectively increased and decreased in all cases compared with the corresponding quantities of bare dhcp Am (0001) surface. The partial charges inside the muffin-tins, difference charge density distributions, and the local density of states have been used to analyze the Am-adatom bond interactions in detail. The implications of chemisorption on Am 5f electron localization-delocalization are also discussed.Comment: 9 Tables, 5 figure

Assessment of Groundwater Quality and its Suitability for Domestic and Agricultural Purposes in parts of the Central Region, Ghana

Groundwater in parts of the Central Region of Ghana was assessed to determine its suitability for domestic use and irrigation activities. Stiff and Piper diagrams show that the predominant water type in the area is Na-Cl, which is characterized by relatively high salinities. This water type occurs in aquifers underlying six coastal districts, namely; Abura-Asebu-Kwamankese (AA), Mfantseman (MF), Gomoa East (GE), Awutu Senya (AwS), Effutu (EF) and Cape Coast (CC). Other water types are Ca-HCO3, Ca-SO4 and Ca-Cl, that occur in districts located further away from the coast. Silicate weathering and ion exchange are identified as the geochemical processes responsible for the various ions in the groundwater. Possible processes that could be responsible for the source of Na+ and Cl- are sea water intrusion and dissolution of minerals. The results also show that the groundwater is mainly supersaturated with respect to both calcite and gypsum, indicating high concentrations of both bicarbonate and sulfate ions in solution. This is associated with considerable enrichment of the groundwater with sulfate, bicarbonate, and calcium ions. On a Wilcox diagram, the groundwater samples, mainly from the districts coded as AA, TLD, AS and AN, which are located away from the coast, plot within the “excellent to good” category, suggesting that water from the area is of acceptable quality for irrigation purposes. Similarly, Sodium Adsorption Ratio (SAR) and conductivity values for the groundwater in the AA, TLD, AS and AN districts indicate low SAR and low to medium salinity respectively. Groundwater in aquifers underlying these districts is therefore suitable for irrigation. Generally, groundwater samples from locations along the coast have high salinity and are not suitable for domestic and irrigation purposes. However, about 72% of the water samples predominantly in districts located away from the sea is suitable for the purposes stated

Density functional study of the actinide nitrides

The full potential all electron linearized augmented plane wave plus local orbitals (FP-LAPW + lo) method, as implemented in the suite of software WIEN2K, has been used to systematically investigate the structural, electronic, and magnetic properties of the actinide compounds AnN (An = Ac, Th, Pa, U, Np, Pu, Am). The theoretical formalism used is the generalized gradient approximation to density functional theory (GGA-DFT) with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional. Each compound has been studied at six levels of theory: non-magnetic (NM), non-magnetic with spin-orbit coupling (NM+SOC), ferromagnetic (FM), ferromagnetic with spin-orbit coupling (FM+SOC), anti-ferromagnetic (AFM), and anti-ferromagnetic with spin-orbit coupling (AFM+SOC). The structural parameters, bulk moduli, densities of states, and charge distributions have been computed and compared to available experimental data and other theoretical calculations published in the literature. The total energy calculations indicate that the lowest energy structures of AcN, ThN, and PaN are degenerate at the NM+SOC, FM+SOC, and AFM+SOC levels of theory with vanishing total magnetic moments in the FM+SOC and AFM+SOC cases, making the ground states essentially non-magnetic with spin-orbit interaction. The ground states of UN, NpN, PuN, and AmN are found to be FM+SOC at the level of theory used in the present computations. The nature of the interactions between the actinide metals and nitrogen atom, and the implications on 5f electron delocalization and localization are discussed in detail.Comment: 5 tables, 12 figure

First-principles simulations of vibrational decay and lifetimes in a -Si:H and a-Si:D

Phonon lifetime in materials is an important observable that conveys basic information about structure, dynamics, and anharmonicity. Recent vibrational transient-grating measurements, using picosecond infrared pulses from free-electron lasers, have demonstrated that the vibrational-population decay rates of localized high-frequency stretching modes (HSMs) in hydrogenated and deuterated amorphous silicon (a-Si:H/D) increase with temperature and the vibrational energy redistributes among the bending modes of Si in a-Si:H/D. Motivated by this observation, we address the problem from first-principles density-functional calculations and study the time evolution of the vibrational-population decay in a-Si:H/D, the average decay times, and the possible decay channels for the redistribution of vibrational energy. The average lifetimes of the localized HSMs in a-Si:H and a-Si:D are found to be approximately 51-92 ps and 50-78 ps, respectively, in the temperature range of 25-200 K, which are consistent with experimental data. A weak temperature dependence of the vibrational-population decay rates has been observed via a slight increase of the decay rates with temperature, which can be attributed to stimulated emission and increased anharmonic coupling between the normal modes at high temperature.The work is partially supported by the U.S. National Science Foundation under Grants No. DMR 1570166, No. DMR 1570118, and No. DMR 1506836. We acknowledge the use of computing resources at the Texas Advanced Computing Center and Ohio Supercomputer Center

Inclusion of Experimental Information in First Principles Modeling of Materials

We propose a novel approach to model amorphous materials using a first principles density functional method while simultaneously enforcing agreement with selected experimental data. We illustrate our method with applications to amorphous silicon and glassy GeSe$_2$. The structural, vibrational and electronic properties of the models are found to be in agreement with experimental results. The method is general and can be extended to other complex materials.Comment: 11 pages, 8 PostScript figures, submitted to J. Phys.: Condens. Matter in honor of Mike Thorpe's 60th birthda

Assessing the applicability of terrestrial laser scanning for mapping englacial conduits

his is an Open Access article, distributed under the terms of the Creative Commons Attribution-NonCommercial-ShareAlike licence (http://creativecommons.org/licenses/by-nc-sa/4.0/), which permits non-commercial re-use, distribution, and reproduction in any medium, provided the same Creative Commons licence is included and the original work is properly cited. The written permission of Cambridge University Press must be obtained for commercial re-use.The morphology of englacial drainage networks and their temporal evolution are poorly characterised, particularly within cold ice masses. At present, direct observations of englacial channels are restricted in both spatial and temporal resolution. Through novel use of a terrestrial laser scanning (TLS) system, the interior geometry of an englacial channel in Austre Brøggerbreen, Svalbard, was reconstructed and mapped. Twenty-eight laser scan surveys were conducted in March 2016, capturing the glacier surface around a moulin entrance and the uppermost 122 m reach of the adjoining conduit. The resulting point clouds provide detailed 3-D visualisation of the channel with point accuracy of 6.54 mm, despite low (<60%) overall laser returns as a result of the physical and optical properties of the clean ice, snow, hoar frost and sediment surfaces forming the conduit interior. These point clouds are used to map the conduit morphology, enabling extraction of millimetre-to-centimetre scale geometric measurements. The conduit meanders at a depth of 48 m, with a sinuosity of 2.7, exhibiting teardrop shaped cross-section morphology. This improvement upon traditional surveying techniques demonstrates the potential of TLS as an investigative tool to elucidate the nature of glacier hydrological networks, through reconstruction of channel geometry and wall composition.Peer reviewedFinal Published versio

Electronic structure and magnetic state of transuranium metals under pressure

Electronic structure of bcc Np, fcc Pu, Am, and Cm pure metals under pressure has been investigated employing the LDA+U method with spin-orbit coupling (LDA+U+SO). Magnetic state of the actinide ions was analyzed in both LS and jj coupling schemes to reveal the applicability of corresponding coupling bases. It was demonstrated that whereas Pu and Am are well described within the jj coupling scheme, Np and Cm can be described appropriately neither in {m-sigma}, nor in {jmj} basis, due to intermediate coupling scheme realizing in these metals that requires some finer treatment. The LDA+U+SO results for the considered transuranium metals reveal bands broadening and gradual 5f electron delocalization under pressure.Comment: 5 pages, 5 figure

Morphology, flow dynamics and evolution of englacial conduits in cold ice

Meltwater routing through ice masses exerts a fundamental control over glacier dynamics and mass balance, and proglacial hydrology. However, despite recent advances in mapping drainage systems in cold, Arctic glaciers, direct observations of englacial channels and their flow conditions remain sparse. Here, using Terrestrial Laser Scanning (TLS) surveys of the main englacial channel of cold-based Austre Brøggerbreen (Svalbard), we map and compare an entrance moulin reach (122 m long) and exit portal reach (273 m long). Analysis of channel planforms, longitudinal profiles, cross-sections and morphological features reveals evidence of spatial variations in water flow conditions and channel incision mechanisms, and the presence of vadose, epiphreatic and phreatic conditions. The entrance reach, located at the base of a perennial moulin, was characterised by vadose, uniform, channel lowering at annual timescales, evidenced by longitudinal grooves, whereas the exit portal reach showed both epiphreatic and vadose conditions, along with upstream knickpoint migration at intra-annual timescales. Fine-scale features, including grooves and scallops, were readily quantified from the TLS point cloud, highlighting the capacity of the technique to inform palaeoflow conditions, and reveal how pulses of meltwater from rainfall events may adjust englacial conduit behaviour. With forecasts of increasing Arctic precipitation in the coming decades, and a progressively greater proportion of glaciers comprising cold ice, augmenting the current knowledge of englacial channel morphology is essential to constrain future glacier hydrological system change

Footballers' Image Rights in the New Media Age

Image rights, broadly defined as the commercial appropriation of someone's personality, including indices of their image, voice, name and signature, have become increasingly important in the political economy of media sport. A range of legal, economic and political arguments have developed in the UK as to what image rights actually are, their legal efficacy and their potential impact on developments in the long-standing relationship between sport and the media. This paper focuses on the problematic definition of the term in the UK context and how it relates to certain economic and commercial transformations in British football. Using the English Premier League and the ‘celebrity footballer’ David Beckham as its primary focus, the paper traces the rise of image rights clauses in player contracts. This process is analysed in the context of rapid and dramatic change in the media coverage of the sport. The paper focuses on the growing legal complexities of protecting star images in relation to the Internet and the wider issues of football, fandom and popular culture