DNS of backward‐facing step flow with fully turbulent inflow

Direct numerical simulation (DNS) has been performed to study the channel flow over a backward‐facing step at a Reynolds number Re_b=5600 based on the step height h and the inflow bulk velocity U_b. A dynamic method has been used in order to generate realistic turbulent inflow conditions. The results upstream of the step compared well with the fully developed channel flow. Downstream of the step our results show excellent agreement with experimental data. Copyright © 2009 John Wiley & Sons, Ltd.     

Relative Oscillation Theory,Weighted Zeros of the Wronskian,and the Spectral Shift Function

We develop an analog of classical oscillation theory for Sturm–Liouville operators which, rather than measuring the spectrum of one single operator, measures the difference between the spectra of two different operators. This is done by replacing zeros of solutions of one operator by weighted zeros of Wronskians of solutions of two different operators. In particular, we show that a Sturm-type comparison theorem still holds in this situation and demonstrate how this can be used to investigate the number of eigenvalues in essential spectral gaps. Furthermore, the connection with Krein’s spectral shift function is established. Research supported by the Austrian Science Fund (FWF) under Grant No. Y330.     

Mass transfer to blood flowing through arterial stenosis

The present investigation deals with a mathematical model representing the mass transfer to blood streaming through the arteries under stenotic condition. The mass transport refers to the movement of atherogenic molecules, that is, blood-borne components, such as oxygen and low-density lipoproteins from flowing blood into the arterial walls or vice versa. The blood flowing through the artery is treated to be Newtonian and the arterial wall is considered to be rigid having differently shaped stenoses in its lumen arising from various types of abnormal growth or plaque formation. The nonlinear unsteady pulsatile flow phenomenon unaffected by concentration-field of the macromolecules is governed by the Navier–Stokes equations together with the equation of continuity while that of mass transfer is controlled by the convection-diffusion equation. The governing equations of motion accompanied by appropriate choice of the boundary conditions are solved numerically by MAC(Marker and Cell) method and checked numerical stability with desired degree of accuracy. The quantitative analysis carried out finally includes the respective profiles of the flow-field and concentration along with their distributions over the entire arterial segment as well. The key factors like the wall shear stress and Sherwood number are also examined for further qualitative insight into the flow and mass transport phenomena through arterial stenosis. The present results show quite consistency with several existing results in the literature which substantiate sufficiently to validate the applicability of the model under consideration.     

ChemInform Abstract: Structure and Conformational Properties of Azido(difluoro)phosphane,F2PN3.

The title compound is characterized by IR (gas phase, Ar matrix), Raman (liquid, amorphous, and crystalline solid), and ¹⁹F, ³¹P, ¹⁴N and ¹⁵N NMR spectroscopy, as well as by quantum chemical DFT calculations.     

Synthesis of room-temperature ionic liquids with the weakly coordinating [Al(ORF)4]- anion (RF=C(H)(CF3)2) and the determination of their principal physical properties

A large series of ionic liquids (ILs) based on the weakly coordinating alkoxyaluminate [Al(hfip)(4)](-) (hfip: hexafluoroisopropoxy) with classical as well as functionalized cations were prepared, and their principal physical properties determined. Melting points are between 0 ([C(4)MMIM][Al(hfip)(4)]) and 69 °C ([C(3)MPip][Al(hfip)(4)]); three qualify as room-temperature ILs (RTILs). Crystal structures for six ILs were determined; their structural parameters and anion-cation contacts are compared here with known ILs, with a special focus on their influence on physical properties. Moreover, the biodegradability of the compounds was investigated by using the closed-bottle and the manometric respirometry test. Temperature-dependent viscosities and conductivities were measured between 0 and 80 °C, and described by either the Vogel-Fulcher-Tammann (VFT) or the Arrhenius equations. Moreover, conductivities and viscosities were investigated in the context of the molecular volume, V(m). Physical property-V(m) correlations were carried out for various temperatures, and the temperature dependence of the molecular volume was analyzed by using crystal structure data and DFT calculations. The IL ionicity was investigated by Walden plots; according to this analysis, [Al(hfip)(4)](-) ILs may be classified as "very good to good ILs"; while [C(2)MIM][Al(hfip)(4)] is a better IL than [C(2)MIM][NTf(2)]. The dielectric constants of ten [Al(hfip)(4)](-) ILs were determined, and are unexpectedly high (ε(r)=11.5 to 16.8). This could be rationalized by considering additional calculated dipole moments of the structures frozen in the solid state by DFT. The determination of hydrogen gas solubility in [Al(hfip)(4)](-) RTILs by high-pressure NMR spectroscopy revealed very high hydrogen solubilities at 25 °C and 1 atm. These results indicate the significant potential of this class of ILs in manifold applications.     

Intermediates Involved in the Oxidation of Nitrogen Monoxide: Photochemistry of the cis‐N2O2⋅O2 complex and of sym‐N2O4 in Solid Ne Matrices

Pure sym‐N₂O₄ isolated in solid Ne was obtained by passing cold neon gas over solid N₂O₄ at ?115 °C and quenching the resulting gaseous mixture at 6.3 K. Filtered UV irradiation (260–400 nm) converts sym‐N₂O₄ into trans‐ONONO₂, a weakly interacting (NO₂)₂ radical pair, and traces of the cis‐N₂O₂?O₂ complex. Besides the weakly bound ON?O₂ complex, cis‐N₂O₂?O₂ was also obtained by co‐deposition of NO and O₂ in solid Ne at 6.3 K, and both complexes were characterised by their matrix IR spectra. Concomitantly formed cis‐N₂O₂ dissociated on exposure to filtered IR irradiation (400–8000 cm^?1), and the cis‐N₂O₂?O₂ complex rearranged to sym‐N₂O₄ and trans‐ONONO₂. Experiments using ¹⁸O₂ in place of ¹⁶O₂ revealed a non‐concerted conversion of cis‐N₂O₂?O₂ into these species, and gave access to four selectively di‐¹⁸O‐substituted trans‐ONONO₂ isotopomers. No isotopic scrambling occurred. The IR spectra of sym‐N₂O₄ and of trans‐ONONO₂ in solid Ne were recorded. IR fundamentals of trans‐ONONO₂ were assigned based on experimental ^16/18O isotopic shifts and guided by DFT calculations. Previously reported contradictory measurements on cis‐ and trans‐ONONO₂ are discussed. Dinitroso peroxide, ONOONO, a proposed intermediate in the IR photoinduced rearrangement of cis‐N₂O₂?O₂ to the various N₂O₄ species, was not detected. Its absence in the photolysis products indicates a low barrier (≤10 kJ mol^?1) for its exothermic O? O bond homolysis into a (NO₂)₂ radical pair.