Hydrogen adsorption on Gd(0001)

The electronic structure of hydrogen adsorbate-induced states on Gd(0001) was investigated by means of photoelectron spectroscopy with linearly polarized radiation. The E vector of the incoming photon beam is rotatable. Clean and well-ordered rare-earth (0001) surfaces exhibit a highly localized surface state near the Fermi edge. After the adsorption of hydrogen, the surface state disappears and an additional sharp feature at about 4 eV binding energy is observed. For this latter state, the ratio of the radial matrix elements as well as the relative phase shifts were determined to be R=R_p/R_f=2.4±0.3 and δ_f−δ_p=310±10°, respectively. The removal of the Gd surface state by hydrogen adsorption was investigated by means of scanning tunneling microscopy (STM) and spectroscopy (STS). The removal of the surface state exhibits domain-like behavior, with surface steps acting as domain boundaries. The tunneling spectra reveal that hydrogen adsorption causes a dramatic reduction in the differential conductivity near the Fermi level.     

Coarse-Grid-CFD for the Thermal Hydraulic Investigation of Rod-Bundles

A nuclear reactor core, that is a few meters in height and diameter is composed of hundreds of fuel assemblies which are again composed of tenth of fuel rods with a diameter of about 10 mm. The relevant length scales for a Computational Fluid Dynamics (CFD) simulations range from the sub millimetre range, relevant for the sub channels up to several meters. Describing such a multi-scale situation with CFD is extremely challenging and the traditional approach is to use integral methods. These are sub channel and sub assembly analyses codes requiring closure by empirical and experimental correlations. A CFD simulation of a complete nuclear reactor set up resolving all relevant scales requires exceedingly large computational resources. However, in many cases there exists repetitive geometrical assemblies and flow patterns. Based on this observation the general approach of creating a parametrized model for a single segment and composing many of these reduced models to obtain the entire reactor simulation becomes feasible. With the Coarse-Grid-CFD (CGCFD) ( [1], [2]), we propose to replace the experimental or empirical input with proper CFD data. Application of the methodology starts with a detailed, well-resolved, and verified CFD simulation of a single representative segment. From this simulation we extract in tabular form so-called volumetric forces which upon parametrization is assigned to all coarse cells. Repeating the fine simulation for multiple flow conditions parametrized data can be obtained or interpolated for all occurring conditions to the desired degree of accuracy. Note, that parametrized data is used to close an otherwise strongly under-resolved, coarsely meshed model of a complete reactor set up. Implementation of volumetric forces are the method of choice to account for effects as long as dominant transport is still distinguishable on the coarse mesh. In cases where smaller scale effects become relevant the Anisotrop Porosity Formulation (APF) allows capturing transport phenomena occurring on the same or slightly smaller scale compared to the coarse mesh resolution. Within this work we present results of several fuel assemblies, that were investigated with our methodology. In particular, we show Coarse-Grid-CFD simulations including a 127 pin LBE cooled wire wrapped fuel assembly. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

EWE: Toward electro-mechanical cardiac simulations with MOOSE

We present the software framework EWE, which is designed for coupled electromechanical simulations in computational cardiology. EWE is build on the multi-physics framework MOOSE. Numerical simulations of coupled problems on an idealized geometry for a left ventricle are shown. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ferromagnetic Ordering in the Layer‐Structured Pd(HS2O7)2

The reaction of (NO₂)(CF₃SO₃) and elemental palladium in oleum (65 % SO₃) leads to violet single crystals of Pd(HS₂O₇)₂ (monoclinic, P2₁/c, Z=2, a=927.80(9), b=682.58(7), c=920.84(9) pm, β=117.756(2)°, wR₂=0.0439). In the crystal structure, the Pd²⁺ ions show an uncommon octahedral coordination of six oxygen atoms belonging to six HS₂O₇^? ions. The linkage of [PdO₆] octahedra and the hydrogendisulfate anions leads to a layer structure, and the layers are held together by hydrogen bonds. The unusual coordination of the Pd²⁺ ions results in an electronic d⁸ high‐spin configuration, which leads to the paramagnetic behavior of the compound. Moreover, at low temperature, a ferromagnetic ordering was observed with a Curie temperature of 8 K.     

Estimating the quadratic covariation of an asynchronously observed semimartingale with jumps

We consider estimation of the quadratic (co)variation of a semimartingale from discrete observations which are irregularly spaced under high-frequency asymptotics. In the univariate setting, results by Jacod for regularly spaced observations are generalized to the case of irregular observations. In the two-dimensional setup under non-synchronous observations, we derive a stable central limit theorem for the Hayashi–Yoshida estimator in the presence of jumps. We reveal how idiosyncratic and simultaneous jumps affect the asymptotic distribution. Observation times generated by Poisson processes are explicitly discussed.     

Electrophysiological Characterization of Transport Across Outer‐Membrane Channels from Gram‐Negative Bacteria in Presence of Lipopolysaccharides

Multi‐drug resistance in Gram‐negative bacteria is often associated with low permeability of the outer membrane. To investigate the role of membrane channels in the uptake of antibiotics, we present an approach using fusion of native outer membrane vesicles (OMVs) into a planar lipid bilayer, allowing characterization of membrane protein channels in their native environment. Two major membrane channels from E. coli, OmpF and OmpC, were overexpressed from the host and the corresponding OMVs were collected. Each OMV fusion surprisingly revealed only single or few channel activities. The asymmetry of the OMVs translates after fusion into the lipid membrane with the lipopolysaccharides (LPS) dominantly present at the side of OMV addition. Compared to the conventional reconstitution method, the channels fused from OMVs containing LPS have similar conductance but a much broader distribution and significantly lower permeation. We suggest using outer membrane vesicles for functional and structural studies of membrane channels in the native membrane.     

Dehydrogenation of dodecahydro-N-ethylcarbazole on Pd/Al2O3 model catalysts

To elucidate the dehydrogenation mechanism of dodecahydro-N-ethylcarbazole (H(12)-NEC) on supported Pd catalysts, we have performed a model study under ultra high vacuum (UHV) conditions. H(12)-NEC and its final dehydrogenation product, N-ethylcarbazole (NEC), were deposited by physical vapor deposition (PVD) at temperatures between 120 K and 520 K onto a supported model catalyst, which consisted of Pd nanoparticles grown on a well-ordered alumina film on NiAl(110). Adsorption and thermally induced surface reactions were followed by infrared reflection absorption spectroscopy (IRAS) and high-resolution X-ray photoelectron spectroscopy (HR-XPS) in combination with density functional theory (DFT) calculations. It was shown that, at 120 K, H(12)-NEC adsorbs molecularly both on the Al(2)O(3)/NiAl(110) support and on the Pd particles. Initial activation of the molecule occurs through C-H bond scission at the 8a- and 9a-positions of the carbazole skeleton at temperatures above 170 K. Dehydrogenation successively proceeds with increasing temperature. Around 350 K, breakage of one C-N bond occurs accompanied by further dehydrogenation of the carbon skeleton. The decomposition intermediates reside on the surface up to 500 K. At higher temperatures, further decay to small fragments and atomic species is observed. These species block most of the absorption sites on the Pd particles, but can be oxidatively removed by heating in oxygen at 600 K, fully restoring the original adsorption properties of the model catalyst.