Radiationless transition probabilities in muonic208Pb,232Th,and238U

The probabilities for non-radiative (n.r.) excitationsP _n.r. in the muonic nuclides²⁰⁸Pb,²³²Th, and²³⁸U have been determined from (μ^?,γγ)-measurements by comparing the intensities of muonic X-ray transitions in single and coincidence spectra. The value ofP _n.r. (3p→1s), measured for the first time, is about 90% for the actinides²³²Th and²³⁸U, but only about 8% for²⁰⁸Pb. The value ofP _n.r. (3d→1s) is found to be 10 % for²³³Th, 13% for²³⁸U, and about 4% for²⁰⁸Pb. For²⁰⁸Pb a vanishing strength of the n.r. decay of the 2p-level is found, while for²³²Th and for²³⁸U n.r. strengths of about 20% and 26%, respectively, are observed. By regarding two subcomplexes of the 2p→1s transitions leading to different mean excitation energies the n.r. transition probabilities were found to be different for²³⁸U only, 21.6% and 31.1.%, respectively.     

Über den Verband der Subnormalteiler einer endlichen,p-auflösbaren Gruppe

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Entmischungserscheinungen in PdB-Legierungen

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What is the role of acid–acid interactions in asymmetric phosphoric acid organocatalysis? A detailed mechanistic study using interlocked and non-interlocked catalysts

Organocatalysis has revolutionized asymmetric synthesis. However, the supramolecular interactions of organocatalysts in solution are often neglected, although the formation of catalyst aggregates can have a strong impact on the catalytic reaction. For phosphoric acid based organocatalysts, we have now established that catalyst–catalyst interactions can be suppressed by using macrocyclic catalysts, which react predominantly in a monomeric fashion, while they can be favored by integration into a bifunctional catenane, which reacts mainly as phosphoric acid dimers. For acyclic phosphoric acids, we found a strongly concentration dependent behavior, involving both monomeric and dimeric catalytic pathways. Based on a detailed experimental analysis, DFT-calculations and direct NMR-based observation of the catalyst aggregates, we could demonstrate that intermolecular acid–acid interactions have a drastic influence on the reaction rate and stereoselectivity of asymmetric transfer-hydrogenation catalyzed by chiral phosphoric acids.

Supramolecular acid–acid interactions lead to competing monomeric and dimeric pathways in phosphoric acid catalysis – so that stereoselectivities depend on catalyst concentration.     

Energy dependence of the charge exchange reaction from muonic hydrogen to oxygen

The charge exchange reaction of negative muons from the atom to oxygen has been measured in gaseous mixtures of H₂ + O₂. The measurements were performed at three different relative oxygen concentrations ranging from 0.2% to 0.8% and total pressures 3.5–15 bar. A mean transfer rate of , describing the transfer from the ground state of thermalized atoms to oxygen, was determined. In order to investigate the energy dependence of the transfer rate, Monte Carlo simulations of the thermalization and the muon transfer were carried out. The comparison of measured and simulated time spectra yielded an epithermal transfer rate =3.9 10¹¹ s^-1 in the energy interval 0.12–0.22 eV. The analysis with the model of Two components shows that all measured time spectra can be reproduced with the same set of parameters.     

Hierarchical self-assembly of aminopyrazole peptides into nanorosettes in water

Self-association of aminopyrazole peptide hybrid 1 leads to stacked nanorosettes. This remarkable, well-ordered structure obeys the laws of nucleic acid self-assembly. In a strictly hierarchical process, formation of aminopyrazole "base" triplets via a hydrogen bond network is accompanied by pi-stacking with a second rosette and final dimerization of two double rosettes to a four-layer superstructure, stabilized by a six-fold half-crown alkylammonium lock. The final complex is soluble in organic as well as in aqueous solution. It was characterized in the solid state by X-ray crystallography, in water by NMR spectroscopy, and in silico by quantum chemical shift calculation. All these methods provide strong evidence for the same hexameric complex geometry. Its structural features bear striking similarity to nucleic acid architectures and their peptidic counterparts, especially alanyl-PNA. The whole self-assembly process is highly solvent- and temperature-dependent and occurs with a high degree of cooperativity--no intermediates are observed. Formation and dissociation of the nanorosette, however, are kinetically slow. The limitation to a hexameric aggregate can be explained by six sterically demanding valine residues, whose replacement by alanines may result in formation of infinite fibers.     

High-Entropy Lithium Argyrodite Solid Electrolytes Enabling Stable All-Solid-State Batteries

Superionic solid electrolytes (SEs) are essential for bulk-type solid-state battery (SSB) applications. Multicomponent SEs are recently attracting attention for their favorable charge-transport properties, however a thorough understanding of how configurational entropy (ΔS_conf) affects ionic conductivity is lacking. Here, we successfully synthesized a series of halogen-rich lithium argyrodites with the general formula Li_5.5PS_4.5Cl_xBr_1.5-x (0≤x≤1.5). Using neutron powder diffraction and ³¹P magic-angle spinning nuclear magnetic resonance spectroscopy, the S²⁻/Cl⁻/Br⁻ occupancy on the anion sublattice was quantitatively analyzed. We show that disorder positively affects Li-ion dynamics, leading to a room-temperature ionic conductivity of 22.7 mS cm⁻¹ (9.6 mS cm⁻¹ in cold-pressed state) for Li_5.5PS_4.5Cl_0.8Br_0.7 (ΔS_conf=1.98R). To the best of our knowledge, this is the first experimental evidence that configurational entropy of the anion sublattice correlates with ion mobility. Our results indicate the possibility of improving ionic conductivity in ceramic ion conductors by tailoring the degree of compositional complexity. Moreover, the Li_5.5PS_4.5Cl_0.8Br_0.7 SE allowed for stable cycling of single-crystal LiNi_0.9Co_0.06Mn_0.04O₂ (s-NCM90) composite cathodes in SSB cells, emphasizing that dual-substituted lithium argyrodites hold great promise in enabling high-performance electrochemical energy storage.     

Secondary ion yields produced by keV atomic and polyatomic ion impacts on a self-assembled monolayer surface

A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd.     

Muon transfer from ground state deuterium to helium nuclei and its temperature dependence

The energy and time distributions of the decay X-rays of excited, metastable, molecular (dμHe)*-resonances were measured. The comparison of the observed energy spectra with calculated ones suggests that decay from the rotational state J = 1 dominates at the investigated conditions. The muon transfer rates from ground state deuterium to the helium isotopes ³He and ⁴He at low temperatures were determined from the time distributions of these spectra. Additionally, the temperature dependence of the muon transfer rate was clearly established in deuterium / ⁴He mixtures. This revised version was published online in August 2006 with corrections to the Cover Date.