Oxygen vacancies versus fluorine at CeO2(111): a case of mistaken identity?

We propose a resolution to the puzzle presented by the surface defects observed with STM at the (111) surface facet of CeO2 single crystals. In the seminal paper of Esch et al. [Science 309, 752 (2005)] they were identified with oxygen vacancies, but the observed behavior of these defects is inconsistent with the results of density functional theory (DFT) studies of oxygen vacancies in the literature. We resolve these inconsistencies via DFT calculations of the properties of both oxygen vacancies and fluorine impurities at CeO2(111), the latter having recently been shown to exist in high concentrations in single crystals from a widely used commercial source of such samples. We find that the simulated filled-state STM images of surface-layer oxygen vacancies and fluorine impurities are essentially identical, which would render problematic their experimental distinction by such images alone. However, we find that our theoretical results for the most stable location, mobility, and tendency to cluster, of fluorine impurities are consistent with experimental observations, in contrast to those for oxygen vacancies. Based on these results, we propose that the surface defects observed in STM experiments on CeO2 single crystals reported heretofore were not oxygen vacancies, but fluorine impurities. Since the similarity of the simulated STM images of the two defects is due primarily to the relative energies of the 2p states of oxygen and fluorine ions, this confusion might also occur for other oxides which have been either doped or contaminated with fluorine

Double exponential stability of quasi-periodic motion in Hamiltonian systems

We prove that generically, both in a topological and measure-theoretical sense, an invariant Lagrangian Diophantine torus of a Hamiltonian system is doubly exponentially stable in the sense that nearby solutions remain close to the torus for an interval of time which is doubly exponentially large with respect to the inverse of the distance to the torus. We also prove that for an arbitrary small perturbation of a generic integrable Hamiltonian system, there is a set of almost full positive Lebesgue measure of KAM tori which are doubly exponentially stable. Our results hold true for real-analytic but more generally for Gevrey smooth systems

Immersed nano-sized Al dispersoids in an Al matrix; effects on the structural and mechanical properties by Molecular Dynamics simulations

We used molecular dynamics simulations based on a potential model in analogy to the Tight Binding scheme in the Second Moment Approximation to simulate the effects of aluminum icosahedral grains (dispersoids) on the structure and the mechanical properties of an aluminum matrix. First we validated our model by calculating several thermodynamic properties referring to the bulk Al case and we found good agreement with available experimental and theoretical data. Afterwards, we simulated Al systems containing Al clusters of various sizes. We found that the structure of the Al matrix is affected by the presence of the dispersoids resulting in well ordered domains of different symmetries that were identified using suitable Voronoi analysis. In addition, we found that the increase of the grain size has negative effect on the mechanical properties of the nanocomposite as manifested by the lowering of the calculated bulk moduli. The obtained results are in line with available experimental data.Comment: 15 pages, 8 figures. Submitted to J. Phys: Condens. Matte

Surface structure and solidification morphology of aluminum nanoclusters

Classical molecular dynamics simulation with embedded atom method potential had been performed to investigate the surface structure and solidification morphology of aluminum nanoclusters Aln (n = 256, 604, 1220 and 2048). It is found that Al cluster surfaces are comprised of (111) and (001) crystal planes. (110) crystal plane is not found on Al cluster surfaces in our simulation. On the surfaces of smaller Al clusters (n = 256 and 604), (111) crystal planes are dominant. On larger Al clusters (n = 1220 and 2048), (111) planes are still dominant but (001) planes can not be neglected. Atomic density on cluster (111)/(001) surface is smaller/larger than the corresponding value on bulk surface. Computational analysis on total surface area and surface energies indicates that the total surface energy of an ideal Al nanocluster has the minimum value when (001) planes occupy 25% of the total surface area. We predict that a melted Al cluster will be a truncated octahedron after equilibrium solidification.Comment: 22 pages, 6 figures, 34 reference

Ultrathin Tropical Tropopause Clouds (UTTCs) : I. Cloud morphology and occurrence

Subvisible cirrus clouds (SVCs) may contribute to dehydration close to the tropical tropopause. The higher and colder SVCs and the larger their ice crystals, the more likely they represent the last efficient point of contact of the gas phase with the ice phase and, hence, the last dehydrating step, before the air enters the stratosphere. The first simultaneous in situ and remote sensing measurements of SVCs were taken during the APE-THESEO campaign in the western Indian ocean in February/March 1999. The observed clouds, termed Ultrathin Tropical Tropopause Clouds (UTTCs), belong to the geometrically and optically thinnest large-scale clouds in the Earth´s atmosphere. Individual UTTCs may exist for many hours as an only 200--300 m thick cloud layer just a few hundred meters below the tropical cold point tropopause, covering up to 105 km2. With temperatures as low as 181 K these clouds are prime representatives for defining the water mixing ratio of air entering the lower stratosphere

Heterogeneous chlorine activation on stratospheric aerosols and clouds in the Arctic polar vortex

Chlorine activation in the Arctic is investigated by examining different parameterizations for uptake coefficients on stratospheric aerosols, high-resolution in-situ measurements and vortex-wide satellite observations. The parameterizations for heterogeneous chemistry on liquid aerosols are most sensitive to temperature with the reaction rates doubling for every 1 K increase in temperature. However, differences between the currently available parameterizations are negligible. For Nitric Acid Trihydrate particles (NAT) the major factors of uncertainty are the number density of nucleated particles and different parameterizations for heterogeneous chemistry. These two factors induce an uncertainty that covers several orders of magnitude on the reaction rate. Nonetheless, since predicted reaction rates on liquid aerosols always exceed those on NAT, the overall uncertainty for chlorine activation is small. In-situ observations of ClO<sub>x</sub> from Arctic winters in 2005 and 2010 are used to evaluate the heterogeneous chemistry parameterizations. The conditions for these measurements proved to be very different between those two winters with HCl being the limiting reacting partner for the 2005 measurements and ClONO<sub>2</sub> for the 2010 measurements. Modeled levels of chlorine activation are in very good agreement with the in-situ observations and the surface area provided by Polar Stratospheric Clouds (PSCs) has only a limited impact on modeled chlorine activation. This indicates that the parameterizations give a good representation of the processes in the atmosphere. Back-trajectories started on the location of the observations in 2005 indicate temperatures on the threshold for PSC formation, hence the surface area is mainly provided by the background aerosol. Still, the model shows additional chlorine activation during this time-frame, providing cautionary evidence for chlorine activation even in the absence of PSCs. Vortex-averaged satellite observations by the MLS instrument also show no definite connection between chlorine activation and PSC formation. The inter -and intra-annual variability of vortex-average HCl and HNO<sub>3</sub> based on MLS observations is examined for the Arctic winters 2004/2005 to 2010/2011. These observations show that removal of HCl and HNO<sub>3</sub> from the gas-phase are not correlated. HNO<sub>3</sub> loss exhibits great inter-annual variability depending on prevailing temperatures while HCl loss is continuous through December without considerable inter- or intra-annual variability. Only the recovery of HCl in late winter depends on the level of denitrification. Hence, the occurrence of HNO<sub>3</sub> containing PSC particles does not seem to have a significant effect on the speed of initial chlorine activation on a vortex-wide scale

Photonuclear Reactions of Three-Nucleon Systems

We discuss the available data for the differential and the total cross section for the photodisintegration of $^3$He and $^3$H and the corresponding inverse reactions below $E_\gamma = 100$ MeV by comparing with our calculations using realistic $NN$ interactions. The theoretical results agree within the errorbars with the data for the total cross sections. Excellent agreement is achieved for the angular distribution in case of $^3$He, whereas for $^3$H a discrepancy between theory and experiment is found.Comment: 11 pages (twocolumn), 12 postscript figures included, uses psfig, RevTe

Comparison of three methods for routine detection of staphylococcus aureus isolated from bovine mastitis

The present study aimed to compare three identification methods that are routinely used for the detection of Staphylococcus aureus as bovine mastitis agent. The evaluated methods were as followed: conventional biochemical method, commercial identification system BioLog (Gen III MicroPlate) and amplification of species-specific gene (nuc) by polymerase chain reaction (PCR). A total of 73 staphylococcal isolates were collected from 453 individual milk samples from dairy cows with subclinical and clinical mastitis from different farms in Bulgaria. This isolates were determined as 60 coagulase-positive, 3 catalase-negative and 10 coagulase-negative by conventional methods. BioLog system identified 72 isolates as S. аureus subsp. aureus and one coagulase-positive isolate as S. schleiferi subsp. coagulans. PCR amplification of nuc gene further confirmed S. аureus subsp. aureus isolates identified by the BioLog system. The primary identification of S. aureus on the basis of coagulase level led to erroneous determination of 14 (19.2%) of the isolates. Based on the findings, BioLog system and PCR appear to be more reliable detection systems for S. aureus from milk. In conclusion, the present study showed that a routine approach using a combination of phenotypic and molecular detection systems could improve S. aureus detection in milk