Structural,Magnetic and Catalytic Properties of a New Vacancy Ordered Perovskite Type Barium Cobaltate BaCoO2.67

A new vacancy ordered, anion deficient perovskite modification with composition of BaCoO_2.67 (Ba₃Co₃O₈□₁) has been prepared via a two-step heating process. Combined Rietveld analysis of neutron and X-ray powder diffraction data shows a novel ordering of oxygen vacancies not known before for barium cobaltates. A combination of neutron powder diffraction, magnetic measurements, and density functional theory (DFT) studies confirms G-type antiferromagnetic ordering. From impedance measurements, the electronic conductivity of the order of 10⁻⁴ S cm⁻¹ is determined. Remarkably, the bifunctional catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is found to be comparable to that of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3–y, confirming that charge-ordered anion deficient non-cubic perovskites can be highly efficient catalysts.     

Spins of the levels and multipole mixing ratios of transitions in 125Sb determined from γ-γ directional correlation and polarization-directional correlation measurements

In order to resolve several discrepancies in spin assignments to levels in ¹²⁵Sb, directional correlations and polarization-directional correlations have been measured for several γ-γ cascades in ¹²⁵Sb populated from the decay of ¹²⁵Sn. Earlier results obtained from using NaI and Ge(Li) and NaI detectors were difficult to interpret due to the complex structure of the decay scheme. To improve the experimental situation, we have used two coaxial Ge(Li) detectors for the angular correlation measurements and a coaxial Ge(Li)-planar Ge(Li) combination for the polarization-directional correlations. Combination of the results of these measurements give unique spin assignments of $\text{11}\text{2}$^?, $\text{11}\text{2}$^?, $\text{9}\text{2}$⁺, $\text{11}\text{2}$⁺ and $\text{9}\text{2}$⁺ to the 1982 keV, 1890 keV, 1420 keV, 1089 keV and 1067 keV levels, respectively. The determined E2/M1 mixing ratios are : δ(470) = 0.010±0.027, δ(1067) = ?0.86±0.18, and δ(916) = ?0.02±0.01.     

Asymmetric hydrogenation of N-sulfonylated-alpha-dehydroamino acids: toward the synthesis of an anthrax lethal factor inhibitor

A novel and highly enantioselective Ru-catalyzed hydrogenation of N-sulfonylated-alpha-dehydroamino acids has been discovered and demonstrated in the synthesis of an anthrax lethal factor inhibitor (LFI). Herein, this methodology is used to prepare N-sulfonylated amino acids in up to 98% ee. This unprecedented hydrogenation uses a chiral Ru catalyst rather than Rh as typical for acylated dehydroamino acids and esters, and this work reports the first asymmetric hydrogenation of a tetrasubstituted dehydroamino acid derivative using a Ru catalyst. [reaction: see text]     

Novel results on structural investigations of natural minerals of clathrate hydrates

High-resolution powder X-ray diffraction measurements were carried out on gas hydrates in the angle-dispersive mode using a synchrotron radiation source. In contrast to the structural studies of laboratory-grown gas hydrates, this study has been performed on naturally grown clathrate hydrates obtained from the sea floor at different geographic locations. While the hydrate samples of the Cascadia Margin exhibit a preponderance of structure I, those from the Gulf of Mexico consist of mixed structures, namely structure II, structure I and structure H. Ice in structure Ih is inherently present in all the clathrate hydrate samples. PACS 61.10.Nz; 61.50.Ah; 61.66.Fn; 91.50.-r     

HREELS investigation of hydrogenated and deuterated GaN{0001} surfaces

The vibrational properties of clean, H- and D-covered GaN{0001} surfaces were investigated by high-resolution electron energy-loss spectroscopy. Auger electron spectroscopy and low-energy electron diffraction were utilized to monitor the surface cleanliness and structure, respectively. At the clean surface the Fuchs-Kliewer surface phonon frequency was determined to 700 cm^-1 (86.8 meV). For the adsorbate-covered surfaces current structure models predict only Ga-H vibrations for surfaces of either polarity. Despite of this, the HREEL-spectra of the hydrogenated sample show a new loss structure at 3255 cm^-1 (403.6 meV) and a shoulder at 1900 cm^-1 (235.6 meV) which are attributed to N-H and Ga-H stretching vibrations, respectively. After deuterium exposure an isotope shift occurs. Again, a N-adsorbate vibration is clearly resolved. A Ga-D bending mode is observed at 390 cm^-1 (48.4 meV), indicating that vibrations of both species are present. Received 1 February 2000     

Effects of Debye shielding in the electron broadening calculations

The impact broadening by charged electron gas is calculated. A proper account of the Debye screening has been taken as also the curvilinearity of the perturber’s trajectories. The results have been given in the form of graphs for a ready comparison with earlier results.