First-principles investigation of Ag-Cu alloy surfaces in an oxidizing environment

In this paper we investigate by means of first-principles density functional theory calculations the (111) surface of the Ag-Cu alloy under varying conditions of pressure of the surrounding oxygen atmosphere and temperature. This alloy has been recently proposed as a catalyst with improved selectivity for ethylene epoxidation with respect to pure silver, the catalyst commonly used in industrial applications. Here we show that the presence of oxygen leads to copper segregation to the surface. Considering the surface free energy as a function of the surface composition, we construct the convex hull to investigate the stability of various surface structures. By including the dependence of the free surface energy on the oxygen chemical potential, we are able compute the phase diagram of the alloy as a function of temperature, pressure and surface composition. We find that, at temperature and pressure typically used in ethylene epoxidation, a number of structures can be present on the surface of the alloy, including clean Ag(111), thin layers of copper oxide and thick oxide-like structures. These results are consistent with, and help explain, recent experimental results.Comment: 10 pages, 6 figure

Electron attachment to SF6 and lifetimes of SF6- negative ions

We study the process of low-energy electron capture by the SF6 molecule. Our approach is based on the model of Gauyacq and Herzenberg [J. Phys. B 17, 1155 (1984)] in which the electron motion is coupled to the fully symmetric vibrational mode through a weakly bound or virtual s state. By tuning the two free parameters of the model, we achieve an accurate description of the measured electron attachment cross section and good agreement with vibrational excitation cross sections of the fully symmetric mode. An extension of the model provides a limit on the characteristic time of intramolecular vibrational relaxation in highly-excited SF6-. By evaluating the total vibrational spectrum density of SF6-, we estimate the widths of the vibrational Feshbach resonances of the long-lived negative ion. We also analyse the possible distribution of the widths and its effect on the lifetime measurements, and investigate nonexponential decay features in metastable SF6-.Comment: 22 pages, 10 figures, submitted to Phys. Rev.

Fragmentation pathways of nanofractal structures on surface

We present a detailed systematical theoretical analysis of the post-growth processes occurring in nanofractals grown on surface. For this study we developed a method which accounts for the internal dynamics of particles in a fractal. We demonstrate that particle diffusion and detachment controls the shape of the emerging stable islands on surface. We consider different scenarios of fractal post-growth relaxation and analyze the time evolution of the island's morphology. The results of our calculations are compared with available experimental observations, and experiments in which the post-growth relaxation of deposited nanostructures can be probed are suggested.Comment: 34 pages, 11 figure

The Effect of the Environment on alpha-Al_2O_3 (0001) Surface Structures

We report that calculating the Gibbs free energy of the alpha-Al_2O_3 (0001) surfaces in equilibrium with a realistic environment containing both oxygen and hydrogen species is essential for obtaining theoretical predictions consistent with experimental observations. Using density-functional theory we find that even under conditions of high oxygen partial pressure, the metal terminated surface is surprisingly stable. An oxygen terminated alpha-Al_2O_3 (0001) surface becomes stable only if hydrogen is present on the surface. In addition, including hydrogen on the surface resolves discrepancies between previous theoretical work and experimental results with respect to the magnitude and direction of surface relaxations.Comment: 4 pages including 2 figures. Submitted to Phys. Rev. Lett. Related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm

Alloy surface segregation in reactive environments: A first-principles atomistic thermodynamics study of Ag3Pd(111) in oxygen atmospheres

We present a first-principles atomistic thermodynamics framework to describe the structure, composition and segregation profile of an alloy surface in contact with a (reactive) environment. The method is illustrated with the application to a Ag3Pd(111) surface in an oxygen atmosphere, and we analyze trends in segregation, adsorption and surface free energies. We observe a wide range of oxygen adsorption energies on the various alloy surface configurations, including binding that is stronger than on a Pd(111) surface and weaker than that on a Ag(111) surface. This and the consideration of even small amounts of non-stoichiometries in the ordered bulk alloy are found to be crucial to accurately model the Pd surface segregation occurring in increasingly O-rich gas phases.Comment: 13 pages including 6 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

A Spatially Resolved `Inside-out' Outburst of IP Pegasi

We present a comprehensive photometric dataset taken over the entire outburst of the eclipsing dwarf nova IP Peg in September/October 1997. Analysis of the lightcurves taken over the long rise to the peak-of-outburst shows conclusively that the outburst started near the centre of the disc and moved outwards. This is the first dataset that spatially resolves such an outburst. The dataset is consistent with the idea that long rise times are indicative of such `inside-out' outbursts. We show how the thickness and the radius of the disc, along with the mass transfer rate change over the whole outburst. In addition, we show evidence of the secondary and the irradiation thereof. We discuss the possibility of spiral shocks in the disc; however we find no conclusive evidence of their existence in this dataset.Comment: 8 pages, 8 figures, to be appear in MNRA

Comparison of Fencing Designs for Excluding Deer from Roadways

We evaluated the efficacy of several fencing designs for restricting movements of 18 captive, female white-tailed deer (Odocoelus virginianus), including standard wovenwire fencing (1.2-m, 1.5-m, 1.8-m, 2.1-m, and 2.4-m tall), opaque fencing (1.2-m, 1.5-m, and 1.8-m tall), and an outrigger fence (i.e., 0.6-m outriggers attached to a 1.2-m-tall wire fence angled at 45º). We recorded the number of successful fence crossings for each deer and characterized behaviors associated with each failed crossing attempt. No deer crossed the 2.4-m fence, whereas all deer crossed the 1.2-m fence. We observed no differences in crossing success between woven-wire and opaque fencing at height

Fibrous Monolithic Ceramics: III, Mechanical Properties and Oxidation Behavior of the Silicon Carbide/Boron Nitride System

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/66176/1/j.1151-2916.1994.tb05399.x.pd

Modeling the impact of sea-spray on particle concentrations in a coastal city

An atmospheric chemistry-transport model is used to assess the impacts of sea-spray chemistry on the particle composition in and downwind of a coastal city--Vancouver, British Columbia. Reactions in/on sea-spray affect the entire particle ensemble and particularly the size distribution of particle nitrate. Urban air quality, and particularly airborne particles, is a major concern in terms of human health impacts. Sea-spray is known to be a major component of the particle ensemble at coastal sites yet relatively few air quality models include the interaction of gases with sea-spray and the fate of the particles produced. Sea-spray is not an inert addition to the particle ensemble because heterogeneous chemistry in/on sea-spray droplets changes the droplets composition and the particle size distribution, which impacts deposition and the ion balance in different particle size fractions. It is shown that the ISOPART model is capable of simulating gas and particle concentrations in the coastal metropolis of Vancouver and the surrounding valley. It is also demonstrated that to accurately simulate ambient concentrations of particles and reactive/soluble gases in a coastal valley it is absolutely critical to include heterogeneous chemistry in/on sea-spray. Partitioning of total particle-NO{sub 3}{sup -} between sea-spray and NH{sub 4}NO{sub 3} is highly sensitive to the amount of sea-spray present, and hence the initial vertical profile, sea-spray source functions [48] and the wind speed. When a fixed wind speed is used to initialize the sea-spray vertical profiles, as expected, the sea-spray concentration decays with distance inland, but the particle-NO{sub 3}{sup -} concentration decays more slowly because it is also a function of the uptake rate for HNO{sub 3}. The simulation results imply model analyses of air quality in coastal cities conducted without inclusion of sea-spray interactions may yield highly misleading results in terms of emission sensitivities of the PM size distribution. The sensitivity of the model results to the initial sea spray profile further suggests there would be great benefit in better definition of the vertical profile of size resolved sea-spray for use in such model studies