Electronic Structure of the Complex Hydride NaAlH4

Density functional calculations of the electronic structure of the complex hydride NaAlH4 and the reference systems NaH and AlH3 are reported. We find a substantially ionic electronic structure for NaAlH4, which emphasizes the importance of solid state effects in this material. The relaxed hydrogen positions in NaAlH4 are in good agreement with recent experiment. The electronic structure of AlH3 is also ionic. Implications for the binding of complex hydrides are discussed.Comment: 4 pages, 5 figure

Multi-phonon scattering and Ti-induced hydrogen dynamics in sodium alanate

We use ab initio methods and neutron inelastic scattering (NIS) to study the structure, energetics, and dynamics of pure and Ti-doped sodium alanate (NaAlH_4), focusing on the possibility of substitutional Ti doping. The NIS spectrum is found to exhibit surprisingly strong and sharp two-phonon features. The calculations reveal that substitutional Ti doping is energetically possible. Ti prefers to substitute for Na and is a powerful hydrogen attractor that facilitates multiple Al--H bond breaking. Our results hint at new ways of improving the hydrogen dynamics and storage capacity of the alanates.Comment: 5 pages, with 4 postscript figures embedded. Uses REVTEX4 and graphicx macro

Structure and Thermodynamics of the Mixed Alkali Alanates

The thermodynamics and structural properties of the hexahydride alanates (M2M'AlH6) with the elpasolite structure have been investigated. A series of mixed alkali alanates (Na2LiAlH6, K2LiAlH6 and K2NaAlH6) were synthesized and found to reversibly absorb and desorb hydrogen without the need for a catalyst. Pressure-composition isotherms were measured to investigate the thermodynamics of the absorption and desorption reactions with hydrogen. Isotherms for catalyzed (4 mol% TiCl3) and uncatalyzed Na2LiAlH6 exhibited an increase in kinetics, but no change in the bulk thermodynamics with the addition of a dopant. A structural analysis using synchrotron x-ray diffraction showed that these compounds favor the Fm-3m space group with the smaller ion (M') occupying an octahedral site. These results demonstrate that appropriate cation substitutions can be used to stabilize or destabilize the material and may provide an avenue to improving the unfavorable thermodynamics of a number of materials with promising gravimetric hydrogen densities.Comment: 6 pages, 7 figures,3 tables, submitted to PR

Chemical Composition, Antioxidant, and Antimicrobial Activities of Lichen Umbilicaria cylindrica (L.) Delise (Umbilicariaceae)

The phytochemical analysis of methanol and chloroform extracts of Umbilicaria cylindrica was determined by HPLC-UV method. The predominant phenolic compound in both extracts was depsidone, salazinic acid (1). Besides salazinic acid, the tested extracts of U. cylindrica contain norstictic acid (2), methyl-β-orcinol carboxylate (3), ethyl haematommate (4), atranorin (5), and usnic acid (6), in different amounts and relations. The lichen extracts showed comparable and strong antioxidant activity, exhibited higher DPPH and hydroxyl radical scavengings, chelating activity, and inhibitory activity towards lipid peroxidation. The lichen extracts demonstrated important antimicrobial activity against eight strains with MIC values from 15.62 to 62.50 μg/mL. This is the first report of the detail chemical composition and antioxidant activity of the lichen Umbilicaria cylindrica, and the results suggest that this lichen can be used as a new source of the natural antioxidants and the substances with antimicrobial features

Electronic structure and optical properties of lightweight metal hydrides

We study the electronic structures and dielectric functions of the simple hydrides LiH, NaH, MgH2 and AlH3, and the complex hydrides Li3AlH6, Na3AlH6, LiAlH4, NaAlH4 and Mg(AlH4)2, using first principles density functional theory and GW calculations. All these compounds are large gap insulators with GW single particle band gaps varying from 3.5 eV in AlH3 to 6.5 eV in the MAlH4 compounds. The valence bands are dominated by the hydrogen atoms, whereas the conduction bands have mixed contributions from the hydrogens and the metal cations. The electronic structure of the aluminium compounds is determined mainly by aluminium hydride complexes and their mutual interactions. Despite considerable differences between the band structures and the band gaps of the various compounds, their optical responses are qualitatively similar. In most of the spectra the optical absorption rises sharply above 6 eV and has a strong peak around 8 eV. The quantitative differences in the optical spectra are interpreted in terms of the structure and the electronic structure of the compounds.Comment: 13 pages, 10 figure

Revisiting dual AGN candidates with spatially resolved LBT spectroscopy: The impact of spillover light contamination

Context. The merging of supermassive black holes (SMBHs) is a direct consequence of our hierarchical picture of galaxy evolution. It is difficult to track the merging process of SMBHs during mergers of galaxies as SMBHs are naturally difficult to observe. Aims. We want to characterise and confirm the presence of two independent active galactic nuclei (AGN) separated by a few kiloparsec in seven strongly interacting galaxies previously selected from the Sloan Digital Sky Survey (SDSS) as Seyfert-Seyfert pairs based on emission-line ratio diagnostics. Methods. Optical slit spectra taken with MODS at the Large Binocular Telescope are presented to infer the detailed spatial distribution of optical emission lines, and their line ratios and AGN signatures with respect to the host galaxies, thereby quantifying the impact of beam smearing and large fibre apertures on the spectra captured by the SDSS. Results. We find that at most two of the seven targets actually retain a Seyfert-Seyfert dual AGN, whereas the others may be more likely powered by post-AGB stars in retired galaxies or through shocks in the ISM based on spatially resolved optical line diagnostics. The major cause of this discrepancy is a bias caused by the spillover of flux from the primary source in the secondary SDSS fibre which can be more than an order of magnitude at < 3\u2033 separations. Previously reported extremely low X-ray-to-[O III] luminosity ratios may be explained by this misclassification, as can heavily obscured AGN for the primaries. We also find that the nuclei with younger stellar ages host the primary AGN. Conclusions. Studies of close dual AGN selected solely from fibre-based spectroscopy can create severe biases in the sample selection and interpretation of the results. Spatially resolved spectroscopy should ideally be used in the future to characterise such compact systems together with multi-wavelength follow-up observations

Discovery of superstrong, fading, iron line emission and double-peaked Balmer lines of the galaxy SDSSJ0952+2143 - the light echo of a huge flare

We report the discovery of superstrong, fading, high-ionization iron line emission in the galaxy SDSSJ095209.56+214313.3 (SDSSJ0952+2143 hereafter), which must have been caused by an X-ray outburst of large amplitude. SDSSJ0952+2143 is unique in its strong multiwavelength variability; such a broadband emission-line and continuum response has not been observed before. The strong iron line emission is accompanied by unusual Balmer line emission with a broad base, narrow core and double-peaked narrow horns, and strong HeII emission. These lines, while strong in the SDSS spectrum taken in 2005, have faded away significantly in new spectra taken in December 2007. Comparison of SDSS, 2MASS, GALEX and follow-up GROND photometry reveals variability in the NUV, optical and NIR band. Taken together, these unusual observations can be explained by a giant outburst in the EUV--X-ray band, detected even in the optical and NIR. The intense and variable iron, Helium and Balmer lines represent the ``light echo'' of the flare, as it traveled through circumnuclear material. The outburst may have been caused by the tidal disruption of a star by a supermassive black hole. Spectroscopic surveys such as SDSS are well suited to detect emission-line light echoes of such rare flare events. Reverberation-mapping of these light echoes can then be used as a new and efficient probe of the physical conditions in the circumnuclear material in non-active or active galaxies.Comment: ApJ Letters, 678, L13 (May 1 issue); incl. 4 colour figures. This and related papers on tidal disruption flares also available at http://www.xray.mpe.mpg.de/~skomossa

Raman study of insulating and conductive ZnO: (Al, Mn) thin films

Raman spectroscopy results obtained for undoped and Al- and/or Mn-doped ZnO thin films produced by RF-sputtering are reported. The effect of the doping method (either co-sputtering or ion implantation), the dopant type and its concentration on the Raman-active vibrational modes in these films were studied in detail. The results are discussed with focus on the peak shifts and broadening, and on the doping-induced relaxation of the symmetry selection rules. A particular attention is paid to the 520-530 cm-1 Raman band observed in all Mn containing samples and a simple theoretical model and arguments are presented in support of its relation to the local (gap) phonon mode produced by Mn atoms substituting Zn in the cationic sublattice of the ZnO crystal.Karlsruhe Nano Micro Facility (KNMF), a Helmholtz Research Infrastructure at KI