Dynamics of bound states of dihydrogen at Cu(I) and Cu(II) species coordinated near one and two zeolite framework aluminium atoms: A combined sorption, INS, IR and DFT study

Abstract Ambient conditions sorption isotherms of dihydrogen in a series of various levels of Cu-exchanged ZSM-5 zeolites, with two different Si/Al ratios, namely 11.5 and 25, show the presence of different amount of Cu centres able to strongly bind H2. Although the isosteric heats of adsorption derived from these isotherms are rather similar, of the order of 30 kJ/mol H2, Inelastic Neutron Scattering (INS) of adsorbed dihydrogen and Fourier-Transformed Infra-Red (FTIR) spectroscopy measurements of adsorbed CO and NO reveal that copper is encountered in two oxidation states. At least two types of Cu(I) ions are clearly detected as well as some heterogeneity of the Cu(II) species. The number of these Cu species is different in the two investigated ZSM-5 materials and depends on the Cu exchange level. With the aid of DFT model cluster calculations we find that under different coordination environments, determined by the Al distribution, both mono- and divalent Cu ions could bind H2 with a different strength. Unprecedentedly, we found that Cu-ions compensating two Al atoms, i.e. formally Cu(II) species, relatively far apart from each other, may behave very similarly to the monovalent Cu-species or alternatively viewed – as Cu(I) species that compensate for two framework Al-atoms. Such Cu-species also form stable η2 dihydrogen complexes

Effect of H on the crystalline and magnetic structures of the YCo3-H(D) system. I. YCo3 from neutron powder diffraction and first-principles calculations

This paper reports investigations into the influence of hydrogen on the magnetic properties of the YCo3-H system. We report results on the magnetic structure and magnetic transitions of YCo3 using a combination of neutron powder diffraction measurements and first-principles full potential augmented plane wave + local orbital calculations under the generalized gradient approximation. The ferromagnetic and ferrimagnetic structures are examined on an equal footing. However, we identify that, no matter which structure is used as the starting point, the neutron diffraction data always refines down to the ferrimagnetic structure with the Co2 atoms having antiparallel spins. In the ab initio calculations, the inclusion of spin-orbit coupling is found to be important in the prediction of the correct magnetic ground state. Here, the results suggest that, for zero external field and sufficiently low temperatures, the spin arrangement of YCo3 is ferrimagnetic rather than ferromagnetic as previously believed. The fixed spin moment calculation technique has been employed to understand the two successive field-induced magnetic transitions observed in previous magnetization measurements under increasing ultrahigh magnetic fields. We find that the magnetic transitions start from the ferrimagnetic phase �0.61�B/Co� and terminate with the ferromagnetic phase �1.16�B/Co�, while the spin on the Co2 atoms progressively changes from antiparallel ferrimagnetic to paramagnetic and then to ferromagnetic. Our neutron diffraction measurements, ab initio calculations, and the high field magnetization measurements are thus entirely self-consistent

Early Ultraviolet, Optical and X-Ray Observations of the Type IIP SN 2005cs in M51 with Swift

We report early photospheric-phase observations of the Type IIP Supernova (SN) 2005cs obtained by Swift's Ultraviolet-Optical and X-Ray Telescopes. Observations started within two days of discovery and continued regularly for three weeks. During this time the V-band magnitude remained essentially constant, while the UV was initially bright but steadily faded until below the brightness of an underlying UV-bright HII region. This UV decay is similar to SNe II observed by the International Ultraviolet Explorer. UV grism spectra show the P-Cygni absorption of MgII 2798A, indicating a photospheric origin of the UV flux. Based on non-LTE model atmosphere calculations with the CMFGEN code, we associate the rapid evolution of the UV flux with the cooling of the ejecta, the peak of the spectral energy distribution (SED) shifting from ~700A on June 30th to ~1200A on July 5th. Furthermore, the corresponding recombination of the ejecta, e.g., the transition from FeIII to FeII, induces considerable strengthening of metal line-blanketing at and above the photosphere, blocking more effectively this fading UV flux. SN2005cs was not detected in X-rays, and the upper limit to the X-ray luminosity yields a limit to the mass loss rate of the progenitor of about 10^-5 solar masses per year. Overall, Swift presents a unique opportunity to capture the early and fast evolution of Type II SNe in the UV, providing additional constraints on the reddening, the SED shortward of 4000A, and the ionization state and temperature of the photon-decoupling regions.Comment: 15 pages, 6 figures. Accepted for publication by Astrophysical Journa

Resist-substrate interface tailoring for generating high density arrays of Ge and Bi2Se3 nanowires by electron beam lithography

The authors report a chemical process to remove the native oxide on Ge and Bi2Se3 crystals, thus facilitating high-resolution electron beam lithography (EBL) on their surfaces using a hydrogen silsesquioxane (HSQ) resist. HSQ offers the highest resolution of all the commercially available EBL resists. However, aqueous HSQ developers such as NaOH and tetramethylammonium hydroxide have thus far prevented the fabrication of high-resolution structures via the direct application of HSQ to Ge and Bi2Se3, due to the solubility of components of their respective native oxides in these strong aqueous bases. Here we provide a route to the generation of ordered, high-resolution, high-density Ge and Bi2Se3 nanostructures with potential applications in microelectronics, thermoelectric, and photonics devices.                        

Using Quantitative Spectroscopic Analysis to Determine the Properties and Distances of Type II-Plateau Supernovae: SNe 2005cs and 2006bp

We analyze the Type II Plateau supernovae (SN II-P) 2005cs and 2006bp with the non-LTE model atmosphere code CMFGEN. We fit 13 spectra in the first month for SN 2005cs and 18 for SN 2006bp. {\sl Swift} ultraviolet photometry and ground-based optical photometry calibrate each spectrum. Our analysis shows both objects were discovered less than 3 days after they exploded, making these the earliest SN II-P spectra ever studied. They reveal broad and very weak lines from highly-ionized fast ejecta with an extremely steep density profile. We identify He{\sc ii} 4686\AA emission in the SN 2006bp ejecta. Days later, the spectra resemble the prototypical Type II-P SN 1999em, which had a supergiant-like photospheric composition. Despite the association of SN 2005cs with possible X-ray emission, the emergent UV and optical light comes from the photosphere, not from circumstellar emission. We surmise that the very steep density fall-off we infer at early times may be a fossil of the combined actions of the shock wave passage and radiation driving at shock breakout. Based on tailored CMFGEN models, the direct-fitting technique and the Expanding Photosphere Method both yield distances and explosion times that agree within a few percent. We derive a distance to NGC 5194, the host of SN 2005cs, of 8.9$\pm$0.5 Mpc and 17.5$\pm$0.8 Mpc for SN 2006bp in NGC 3953. The luminosity of SN 2006bp is 1.5 times that of SN 1999em, and 6 times that of SN 2005cs. Reliable distances to Type II-P supernovae that do not depend on a small range in luminosity provide an independent route to the Hubble Constant and improved constraints on other cosmological parameters.Comment: 27 pages, 16 figures, 11 tables, accepted to ApJ, high-resolution of the paper available at http://hermes.as.arizona.edu/~luc/snIIP/sn05cs_06bp.ps.g

Bonobos Maintain Immune System Diversity with Three Functional Types of MHC-B

Fast-evolving MHC class I polymorphism serves to diversify NK cell and CD8 T cell responses in individuals, families, and populations. Because only chimpanzee and bonobo have strict orthologs of all HLA class I, their study gives unique perspectives on the human condition. We defined polymorphism of Papa-B, the bonobo ortholog of HLA-B, for six wild bonobo populations. Sequences for Papa-B exon 2 and 3 were determined from the genomic DNA in 255 fecal samples, minimally representing 110 individuals. Twenty-two Papa-B alleles were defined, each encoding a different Papa-B protein. No Papa-B is identical to any chimpanzee Patr-B, human HLA-B, or gorilla Gogo-B. Phylogenetic analysis identified a Glade of MHC-B, defined by residues 45-74 of the alpha(1) domain, which is broadly conserved among bonobo, chimpanzee, and gorilla. Bonobo populations have 3-14 Papa-B allotypes. Three Papa-B are in all populations, and they are each of a different functional type: allotypes having the Bw4 epitope recognized by killer cell Ig-like receptors of NK cells, allotypes having the Cl epitope also recognized by killer cell Ig-like receptors, and allotypes having neither epitope. For population Malebo, these three Papa-B are the only Papa-B allotypes. Although small in number, their sequence divergence is such that the nucleotide diversity (mean proportional distance) of Papa-B in Malebo is greater than in the other populations and is also greater than expected for random combinations of three Papa-B. Overall, Papa-B has substantially less diversity than Patr-B in chimpanzee subspecies and HLA-B in indigenous human populations, consistent with bonobo having experienced narrower population bottlenecks

International Trade Under the Rule of Law Conference

The central focus of the conference was the dispute settlement system of the World Trade Organization (WTO), with a view toward exploring the need for a superstructure of international law governing trade and economic cooperation between countries

No. 5 - International Trade under the Rule of Law: An American Society of International Law Centennial Regional Meeting

Organized and sponsored by the Dean Rusk Center and designated an American Society of International Law Centennial Regional Meeting, this conference focused on the Dispute Settlement System (DSS) of the World Trade Organization (WTO) with a view toward discussing the need for a superstructure of international law governing trade and economic cooperation between states

Infrared seeded parametric four-wave mixing for sensitive detection of molecules

We have developed a sensitive resonant four-wave mixing technique based on two-photon parametric four-wave mixing with the addition of a phase matched ''seeder'' field. Generation of the seeder field via the same four-wave mixing process in a high pressure cell enables automatic phase matching to be achieved in a low pressure sample cell. This arrangement facilitates sensitive detection of complex molecular spectra by simply tuning the pump laser. We demonstrate the technique with the detection of nitric oxide down to concentrations more than 4 orders of magnitude below the capability of parametric four-wave mixing alone, with an estimated detection threshold of 10(12) molecules/cm(3)

LBT/ARGOS adaptive optics observations of z∼2\sim 2 lensed galaxies

Gravitationally lensed systems allow a detailed view of galaxies at high redshift. High spatial- and spectral-resolution measurements of arc-like structures can offer unique constraints on the physical and dynamical properties of high-z systems. We present near-infrared spectra centred on the gravitational arcs of six known z ~ 2 lensed star-forming galaxies of stellar masses of 10^9-10^11 Msun and star formation rate (SFR) in the range between 10 and 400 Msun/yr. Ground layer adaptive optics (AO)-assisted observations are obtained at the Large Binocular Telescope (LBT) with the LUCI spectrographs during the commissioning of the ARGOS facility. We used MOS masks with curved slits to follow the extended arched structures and study the diagnostic emission lines. Combining spatially resolved kinematic properties across the arc-like morphologies, emission line diagnostics and archival information, we distinguish between merging and rotationally supported systems, and reveal the possible presence of ejected gas. For galaxies that have evidence for outflows, we derive outflow energetics and mass-loading factors compatible with those observed for stellar winds in local and high-z galaxies. We also use flux ratio diagnostics to derive gas-phase metallicities. The low signal-to-noise ratio in the faint H$\beta$ and nitrogen lines allows us to derive an upper limit of ~ 0.15 dex for the spatial variations in metallicity along the slit for the lensed galaxy J1038. Analysed near-infrared spectra presented here represent the first scientific demonstration of performing AO-assisted multi-object spectroscopy with narrow curved-shape slits. The increased angular and spectral resolution, combined with the binocular operation mode with the 8.4-m-wide eyes of LBT, will allow the characterisation of kinematic and chemical properties of a large sample of galaxies at high-z in the near future.Comment: 18 pages, 13 figures, accepted for publication in A&