Polyhedral units and network connectivity in calcium aluminosilicate glasses from high-energy x-ray diffraction

Structure factors for Cax/2AlxSi1-xO2 glasses (x=0,0.25,0.5,0.67) extended to a wave vector of magnitude Q= 40 1/A have been obtained by high-energy x-ray diffraction. For the first time, it is possible to resolve the contributions of Si-O, Al-O and Ca-O coordination polyhedra to the experimental atomic pair distribution functions (PDF). It has been found that both Si and Al are four-fold coordinated and so participate in a continuous tetrahedral network at low values of x. The number of network breaking defects in the form of non-bridging oxygens (NBO's) increases slowly with x until x=0.5 (NBO's ~ 10% at x=0.5). By x=0.67 the network breaking defects become significant as evidenced by the significant drop in the average coordination number of Si. By contrast, Al-O tetrahedra remain free of NBO's and fully integrated in the Al/Si-O network for all values of x. Calcium maintains a rather uniform coordination sphere of approximately 5 oxygen atoms for all values of x. The results suggest that not only Si/Al-O tetrahedra but Ca-O polyhedra, too, play a role in determining the glassy structure

Systematic study of deformed nuclei at the drip lines and beyond

An improved prescription for choosing a transformed harmonic oscillator (THO) basis for use in configuration-space Hartree-Fock-Bogoliubov (HFB) calculations is presented. The new HFB+THO framework that follows accurately reproduces the results of coordinate-space HFB calculations for spherical nuclei, including those that are weakly bound. Furthermore, it is fully automated, facilitating its use in systematic investigations of large sets of nuclei throughout the periodic table. As a first application, we have carried out calculations using the Skyrme Force SLy4 and volume pairing, with exact particle number projection following application of the Lipkin-Nogami prescription. Calculations were performed for all even-even nuclei from the proton drip line to the neutron drip line having proton numbers Z=2,4,...,108 and neutron numbers N=2,4,...,188. We focus on nuclei near the neutron drip line and find that there exist numerous particle-bound even-even nuclei (i.e., nuclei with negative Fermi energies) that have at the same time negative two-neutron separation energies. This phenomenon, which was earlier noted for light nuclei, is attributed to bound shape isomers beyond the drip line.Comment: 12 ReVTeX4 pages, 6 EPS figures. See also http://www.fuw.edu.pl/~dobaczew/thodri/thodri.htm

Average ground-state energy of finite Fermi systems

Semiclassical theories like the Thomas-Fermi and Wigner-Kirkwood methods give a good description of the smooth average part of the total energy of a Fermi gas in some external potential when the chemical potential is varied. However, in systems with a fixed number of particles N, these methods overbind the actual average of the quantum energy as N is varied. We describe a theory that accounts for this effect. Numerical illustrations are discussed for fermions trapped in a harmonic oscillator potential and in a hard wall cavity, and for self-consistent calculations of atomic nuclei. In the latter case, the influence of deformations on the average behavior of the energy is also considered.Comment: 10 pages, 8 figure

Evidence for shape coexistence in 98^{98}Mo

A $\gamma\gamma$ angular correlation experiment has been performed to investigate the low-energy states of the nucleus $^{98}$Mo. The new data, including spin assignments, multipole mixing ratios and lifetimes reveal evidence for shape coexistence and mixing in $^{98}$Mo, arising from a proton intruder configuration. This result is reproduced by a theoretical calculation within the proton-neutron interacting boson model with configuration mixing, based on microscopic energy density functional theory. The microscopic calculation indicates the importance of the proton particle-hole excitation across the Z=40 sub-shell closure and the subsequent mixing between spherical vibrational and the $\gamma$-soft equilibrium shapes in $^{98}$Mo.Comment: 6 pages, 5 figures, 3 tables; published in Phys. Rev.

Thirteen years of integrated precipitable water derived by GPS at Mario Zucchelli Station, Antarctica

Since 1998, the Italian Antarctic Programme is funding space geodetic activities based on the use of episodic and permanent GPS observations. Beside their exploitation in geodynamics, the data can be used to sense the atmosphere and retrieve the water vapour content and variation. The surface pressure and temperature at the GPS tracking sites are necessary to compute the precipitable water; at sites where no information is available, the values can be retrieved from a global grid model. We process the data series of the permanent GPS site TNB1 (Mario Zucchelli Station, Antarctica) from 1998 up to 2010 comparing the use of grid values to the implementation of real surface records. With both approaches, we estimate almost 70000 hourly values of precipitable water over 13 years and we find discrepancies varying between (1.8 ± 0.2) mm in summer and (3.3 ± 0.5) mm in winter. In addition, the discrepancies of the two solutions exhibit a clear seasonal dependency. We validate our results using radio soundings measurements. They agree better with the precipitable water values derived from real surface data. Nevertheless, these latter exhibit dry biases and detect the (77±21) % of the content of moisture measured by the radio soundings. Both GPS and radio sounding observations are processed adopting the most up-to-date strategies to reduce and dominate known systematic errors

Oxide-Supported IrNiO_x Core-Shell Particles as Efficient, Cost-Effective, and Stable Catalysts for Electrochemical Water Splitting

Active and highly stable oxide-supported IrNiOx core–shell catalysts for electrochemical water splitting are presented. IrNix@IrOx nanoparticles supported on high-surface-area mesoporous antimony-doped tin oxide (IrNiOx /Meso-ATO) were synthesized from bimetallic IrNix precursor alloys (PA-IrNix /Meso-ATO) using electrochemical Ni leaching and concomitant Ir oxidation. Special emphasis was placed on Ni/NiO surface segregation under thermal treatment of the PA-IrNix /Meso-ATO as well as on the surface chemical state of the particle/oxide support interface. Combining a wide array of characterization methods, we uncovered the detrimental effect of segregated NiO phases on the water splitting activity of core–shell particles. The core–shell IrNiOx /Meso-ATO catalyst displayed high water-splitting activity and unprecedented stability in acidic electrolyte providing substantial progress in the development of PEM electrolyzer anode catalysts with drastically reduced Ir loading and significantly enhanced durability

Evidence for charge localization in the ferromagnetic phase of La_(1-x)Ca_(x)MnO_3 from High real-space-resolution x-ray diffraction

High real-space-resolution atomic pair distribution functions of La_(1-x)Ca_(x)MnO_3 (x=0.12, 0.25 and 0.33) have been measured using high-energy x-ray powder diffraction to study the size and shape of the MnO_6 octahedron as a function of temperature and doping. In the paramagnetic insulating phase we find evidence for three distinct bond-lengths (~ 1.88, 1.95 and 2.15A) which we ascribe to Mn^{4+}-O, Mn^{3+}-O short and Mn^{3+}-O long bonds respectively. In the ferromagnetic metallic (FM) phase, for x=0.33 and T=20K, we find a single Mn-O bond-length; however, as the metal-insulator transition is approached either by increasing T or decreasing x, intensity progressively appears around r=2.15 and in the region 1.8 - 1.9A suggesting the appearance of Mn^{3+}-O long bonds and short Mn^{4+}-O bonds. This is strong evidence that charge localized and delocalized phases coexist close to the metal-insulator transition in the FM phase.Comment: 8 pages, 8 postscript figures, submitted to Phys. Rev.

Density functional theory and Kohn-Sham scheme for self-bound systems

We demonstrate how the separation of the total energy of a self-bound system into a functional of the internal one-body Fermionic density and a function of an arbitrary wave vector describing the center-of-mass kinetic energy can be used to set-up an "internal" Kohn-Sham scheme.Comment: 6 pages. To be published in Phys. Rev.

High real-space resolution measurement of the local structure of Ga_1-xIn_xAs using x-ray diffraction

High real-space resolution atomic pair distribution functions (PDF)s from the alloy series Ga_1-xIn_xAs have been obtained using high-energy x-ray diffraction. The first peak in the PDF is resolved as a doublet due to the presence of two nearest neighbor bond lengths, Ga-As and In-As, as previously observed using XAFS. The widths of nearest, and higher, neighbor pairs are analyzed by separating the strain broadening from the thermal motion. The strain broadening is five times larger for distant atomic neighbors as compared to nearest neighbors. The results are in agreement with model calculations.Comment: 4 pages, 5 figure