Homogeneous Gold Catalysis through Relativistic Effects: Addition of Water to Propyne

In the catalytic addition of water to propyne the Au(III) catalyst is not stable under non-relativistic conditions and dissociates into a Au(I) compound and Cl2. This implies that one link in the chain of events in the catalytic cycle is broken and relativity may well be seen as the reason why Au(III) compounds are effective catalysts.Comment: 12 pages, 3 figures, 1 tabl

Strain bursts in plastically deforming Molybdenum micro- and nanopillars

Plastic deformation of micron and sub-micron scale specimens is characterized by intermittent sequences of large strain bursts (dislocation avalanches) which are separated by regions of near-elastic loading. In the present investigation we perform a statistical characterization of strain bursts observed in stress-controlled compressive deformation of monocrystalline Molybdenum micropillars. We characterize the bursts in terms of the associated elongation increments and peak deformation rates, and demonstrate that these quantities follow power-law distributions that do not depend on specimen orientation or stress rate. We also investigate the statistics of stress increments in between the bursts, which are found to be Weibull distributed and exhibit a characteristic size effect. We discuss our findings in view of observations of deformation bursts in other materials, such as face-centered cubic and hexagonal metals.Comment: 14 pages, 8 figures, submitted to Phil Ma

Identification of the slow E3 transition 136mCs -> 136Cs with conversion electrons

We performed at ISOLDE the spectroscopy of the decay of the 8- isomer in 136Cs by and conversion-electron detection. For the first time the excitation energy of the isomer and the multipolarity of its decay have been measured. The half-life of the isomeric state was remeasured to T1/2 = 17.5(2) s. This isomer decays via a very slow 518 keV E3 transition to the ground state. In addition to this, a much weaker decay branch via a 413 keV M4 and a subsequent 105 keV E2 transition has been found. Thus we have found a new level at 105 keV with spin 4+ between the isomeric and the ground state. The results are discussed in comparison to shell model calculations.Comment: Phys. Rev. C accepted for publicatio

First identification of large electric monopole strength in well-deformed rare earth nuclei

Excited states in the well-deformed rare earth isotopes $^{154}$Sm and $^{166}$Er were populated via ``safe'' Coulomb excitation at the Munich MLL Tandem accelerator. Conversion electrons were registered in a cooled Si(Li) detector in conjunction with a magnetic transport and filter system, the Mini-Orange spectrometer. For the first excited $0^+$ state in $^{154}$Sm at 1099 keV a large value of the monopole strength for the transition to the ground state of $\rho^2(\text{E0}; 0^+_2 \to 0^+_\text{g}) = 96(42)\cdot 10^{-3}$ could be extracted. This confirms the interpretation of the lowest excited $0^+$ state in $^{154}$Sm as the collective $\beta$-vibrational excitation of the ground state. In $^{166}$Er the measured large electric monopole strength of $\rho^2(\text{E0}; 0^+_4 \to 0^+_1) = 127(60)\cdot 10^{-3}$ clearly identifies the $0_4^+$ state at 1934 keV to be the $\beta$-vibrational excitation of the ground state.Comment: submitted to Physics Letters

From sticky-hard-sphere to Lennard-Jones-type clusters.

A relation M_{SHS→LJ} between the set of nonisomorphic sticky-hard-sphere clusters M_{SHS} and the sets of local energy minima M_{LJ} of the (m,n)-Lennard-Jones potential V_{mn}^{LJ}(r)=ɛ/n-m[mr^{-n}-nr^{-m}] is established. The number of nonisomorphic stable clusters depends strongly and nontrivially on both m and n and increases exponentially with increasing cluster size N for N≳10. While the map from M_{SHS}→M_{SHS→LJ} is noninjective and nonsurjective, the number of Lennard-Jones structures missing from the map is relatively small for cluster sizes up to N=13, and most of the missing structures correspond to energetically unfavorable minima even for fairly low (m,n). Furthermore, even the softest Lennard-Jones potential predicts that the coordination of 13 spheres around a central sphere is problematic (the Gregory-Newton problem). A more realistic extended Lennard-Jones potential chosen from coupled-cluster calculations for a rare gas dimer leads to a substantial increase in the number of nonisomorphic clusters, even though the potential curve is very similar to a (6,12)-Lennard-Jones potential.epsr

Excited States of Ladder-type Poly-p-phenylene Oligomers

Ground state properties and excited states of ladder-type paraphenylene oligomers are calculated applying semiempirical methods for up to eleven phenylene rings. The results are in qualitative agreement with experimental data. A new scheme to interpret the excited states is developed which reveals the excitonic nature of the excited states. The electron-hole pair of the S1-state has a mean distance of approximately 4 Angstroem.Comment: 24 pages, 21 figure

Yielding and irreversible deformation below the microscale: Surface effects and non-mean-field plastic avalanches

Nanoindentation techniques recently developed to measure the mechanical response of crystals under external loading conditions reveal new phenomena upon decreasing sample size below the microscale. At small length scales, material resistance to irreversible deformation depends on sample morphology. Here we study the mechanisms of yield and plastic flow in inherently small crystals under uniaxial compression. Discrete structural rearrangements emerge as series of abrupt discontinuities in stress-strain curves. We obtain the theoretical dependence of the yield stress on system size and geometry and elucidate the statistical properties of plastic deformation at such scales. Our results show that the absence of dislocation storage leads to crucial effects on the statistics of plastic events, ultimately affecting the universal scaling behavior observed at larger scales.Comment: Supporting Videos available at http://dx.plos.org/10.1371/journal.pone.002041

Comparison of the atmosphere above the South Pole, Dome C and Dome A: first attempt

The atmospheric properties above three sites (Dome C, Dome A and the South Pole) on the Internal Antarctic Plateau are investigated for astronomical applications using the monthly median of the analyses from ECMWF (the European Centre for Medium-Range Weather Forecasts). Radiosoundings extended on a yearly time scale at the South Pole and Dome C are used to quantify the reliability of the ECMWF analyses in the free atmosphere as well as in the boundary and surface layers, and to characterize the median wind speed in the first 100 m above the two sites. Thermodynamic instability properties in the free atmosphere above the three sites are quantified with monthly median values of the Richardson number. We find that the probability to trigger thermodynamic instabilities above 100 m is smaller on the Internal Antarctic Plateau than on mid-latitude sites. In spite of the generally more stable atmospheric conditions of the Antarctic sites compared to mid-latitude sites, Dome C shows worse thermodynamic instability conditions than those predicted above the South Pole and Dome A above 100 m. A rank of the Antarctic sites done with respect to the strength of the wind speed in the free atmosphere (ECMWF analyses) as well as the wind shear in the surface layer (radiosoundings) is presented.Comment: Accepted for publishing in MNRAS. 14 pages, 10 figures. The definitive version is available at http://www.blackwell-synergy.co