Acoustic simulations with higher order finite and infinite elements

The efficiency of finite element based simulations of Helmholtz problems is primarily affected by two facts. First, the numerical solution suffers from the so-called pollution effect, which leads to very high element resolutions at higher frequencies. Furthermore, the spectral properties of the resulting system matrices, and hence the convergence of iterative solvers, deteriorate with increasing wave numbers. In this contribution the influence of different types of polynomial basis functions on the efficiency and stability of interior as well as exterior acoustic simulations is analyzed. The current investigations show that a proper choice for the polynomial shape approximation may significantly increase the performance of Krylov subspace methods. In particular, the efficiency of higher order finite and infinite elements based on Bernstein polynomial shape approximation and the corresponding iterative solution strategies is assessed for practically relevant numerical examples including the sound radiation from rolling vehicle tires. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Initiation of Radical Chain Reactions of Thiol Compounds and Alkenes without any Added Initiator: Thiol‐Catalyzed cis/trans Isomerization of Methyl Oleate

A kinetic study of the dodecanethiol‐catalyzed cis/trans isomerization of methyl oleate (cis‐ 2 ) without added initiator was performed by focusing on the initiation of the radical chain reaction. The reaction orders of the rate of isomerization were 2 and 0.5 for 1 and cis‐ 2 , respectively, and an overall kinetic isotope effect k_H/k_D of 2.8 was found. The initiation was shown to be a complex reaction. The electron‐donor/‐acceptor (EDA) complex of dodecanethiol ( 1 ) and cis‐ 2 formed in a pre‐equilibrium reacts with thiol 1 to give a stearyl and a sulfuranyl radical through molecule‐assisted homolysis (MAH) of the sulfur–hydrogen bond. Fragmentation of the latter gives the thiyl radical, which catalyzes the cis/trans isomerization. A computational study of the EDA complex, MAH reaction, and the sulfuranyl radical calculated that the activation energy of the isomerization was in good agreement with the experimental result of E_A=82 kJ M ^?1. Overall, the results may explain that the thermal generation of thiyl radicals without any initiator is responsible for many well‐known thermally initiated addition reactions of thiol compounds to alkenes and their respective polymerizations and for the low shelf‐life stability of cis‐unsaturated thiol compounds and of mixtures of alkenes and thiol compounds.     

Cellular Structure on the Minimal Resolution of the Edge Ideal of the Complement of the n-Cycle

We study the minimal free resolution of the edge ideal of the complement of the n-cycle for n ≥ 4 and construct a regular cellular complex which supports this resolution.     

Initiation of radical chain reactions of thiol compounds and alkenes without any added initiator: thiol-catalyzed cis/trans isomerization of methyl oleate

A kinetic study of the dodecanethiol-catalyzed cis/trans isomerization of methyl oleate (cis-2) without added initiator was performed by focusing on the initiation of the radical chain reaction. The reaction orders of the rate of isomerization were 2 and 0.5 for 1 and cis-2, respectively, and an overall kinetic isotope effect k(H)/k(D) of 2.8 was found. The initiation was shown to be a complex reaction. The electron-donor/-acceptor (EDA) complex of dodecanethiol (1) and cis-2 formed in a pre-equilibrium reacts with thiol 1 to give a stearyl and a sulfuranyl radical through molecule-assisted homolysis (MAH) of the sulfur-hydrogen bond. Fragmentation of the latter gives the thiyl radical, which catalyzes the cis/trans isomerization. A computational study of the EDA complex, MAH reaction, and the sulfuranyl radical calculated that the activation energy of the isomerization was in good agreement with the experimental result of E(A)=82?kJ M(-1). Overall, the results may explain that the thermal generation of thiyl radicals without any initiator is responsible for many well-known thermally initiated addition reactions of thiol compounds to alkenes and their respective polymerizations and for the low shelf-life stability of cis-unsaturated thiol compounds and of mixtures of alkenes and thiol compounds.     

Oils and fats as renewable raw materials in chemistry

Oils and fats of vegetable and animal origin have been the most important renewable feedstock of the chemical industry in the past and in the present. A tremendous geographical and feedstock shift of oleochemical production has taken place from North America and Europe to southeast Asia and from tallow to palm oil. It will be important to introduce and to cultivate more and new oil plants containing fatty acids with interesting and desired properties for chemical utilization while simultaneously increasing the agricultural biodiversity. The problem of the industrial utilization of food plant oils has become more urgent with the development of the global biodiesel production. The remarkable advances made during the last decade in organic synthesis, catalysis, and biotechnology using plant oils and the basic oleochemicals derived from them will be reported, including, for example, ω‐functionalization of fatty acids containing internal double bonds, application of the olefin metathesis reaction, and de novo synthesis of fatty acids from abundantly available renewable carbon sources.     

Reduced effective spin-orbital degeneracy and spin-orbital ordering in paramagnetic transition-metal oxides: Sr2IrO4 versus Sr2RhO4

We discuss the notions of spin-orbital polarization and ordering in paramagnetic materials, and address their consequences in transition-metal oxides. Extending the combined density functional and dynamical mean field theory scheme to the case of materials with large spin-orbit interactions, we investigate the electronic excitations of the paramagnetic phases of Sr(2)IrO(4) and Sr(2)RhO(4). We show that the interplay of spin-orbit interactions, structural distortions and Coulomb interactions suppresses spin-orbital fluctuations. As a result, the room temperature phase of Sr(2)IrO(4) is a paramagnetic spin-orbitally ordered Mott insulator. In Sr(2)RhO(4), the effective spin-orbital degeneracy is reduced, but the material remains metallic, due to both, smaller spin-orbit and smaller Coulomb interactions. The corresponding spectra are in excellent agreement with photoemission data. Finally, we make predictions for the spectra of paramagnetic Sr(2)IrO(4).     

Review: Experiments in Fundamental Physics Scheduled and in Development for the ISS

This is a review of those experiments in the area of Fundamental Physics that are either approved by ESA and NASA, or are currently under development, which are to be performed in the microgravity environment of the International Space Station. These experiments cover the physics of liquid Helium (SUE, BEST, MISTE, DYNAMX, and EXACT), ultrastable atomic clocks (PHARAO, PARCS, RACE), ultrastable microwave resonators (SUMO), and particle detectors (AMS and EUSO). The scientific goals are to study more precisely the universality properties of liquid Helium under microgravity conditions, to establish better time standards and to test the universality of the gravitational red shift, to make more precise tests of the constancy of the speed of light, and to measure the particle content in space directly without disturbances from the Earth's inner atmosphere.     

Observation of Hubbard bands in γ-manganese

JETP Letters - We present angle-resolved photoemission spectra of the γ phase of manganese as well as a theoretical analysis using a recently developed approach that combines density...