Electronic structure and the glass transition in pnictide and chalcogenide semiconductor alloys. Part I: The formation of the ppσpp\sigma-network

Semiconductor glasses exhibit many unique optical and electronic anomalies. We have put forth a semi-phenomenological scenario (J. Chem. Phys. 132, 044508 (2010)) in which several of these anomalies arise from deep midgap electronic states residing on high-strain regions intrinsic to the activated transport above the glass transition. Here we demonstrate at the molecular level how this scenario is realized in an important class of semiconductor glasses, namely chalcogen and pnictogen containing alloys. Both the glass itself and the intrinsic electronic midgap states emerge as a result of the formation of a network composed of $\sigma$-bonded atomic $p$-orbitals that are only weakly hybridized. Despite a large number of weak bonds, these $pp\sigma$-networks are stable with respect to competing types of bonding, while exhibiting a high degree of structural degeneracy. The stability is rationalized with the help of a hereby proposed structural model, by which $pp\sigma$-networks are symmetry-broken and distorted versions of a high symmetry structure. The latter structure exhibits exact octahedral coordination and is fully covalently-bonded. The present approach provides a microscopic route to a fully consistent description of the electronic and structural excitations in vitreous semiconductors.Comment: 22 pages, 17 figures, revised version, final version to appear in J. Chem. Phy

Mixed valency in cerium oxide crystallographic phases: Determination of valence of the different cerium sites by the bond valence method

We have applied the bond valence method to cerium oxides to determine the oxidation states of the Ce ion at the various site symmetries of the crystals. The crystals studied include cerium dioxide and the two sesquioxides along with some selected intermediate phases which are crystallographically well characterized. Our results indicate that cerium dioxide has a mixed-valence ground state with an f-electron population on the Ce site of 0.27 while both the A- and C-sesquioxides have a nearly pure f^1 configuration. The Ce sites in most of the intermediate oxides have non-integral valences. Furthermore, many of these valences are different from the values predicted from a naive consideration of the stoichiometric valence of the compound

New Limits to the Infrared Background: Bounds on Radiative Neutrino Decay and on Contributions of Very Massive Objects to the Dark Matter Problem

From considering the effect of γ-γ interactions on recently observed TeV gamma-ray spectra, improved limits are set to the density of extragalactic infrared photons which are robust and essentially model independent. The resulting limits are more than an order of magnitude more restrictive than direct observations in the 0.025–0.3 eV regime. These limits are used to improve constraints on radiative neutrino decay in the mass range above 0.05 eV and to rule out very massive objects as providing the dark matter needed to explain galaxy rotation curves. Lower bounds on the maximum distance which TeV gamma rays may probe are also derived

Tev Observations of the Variability and Spectrum of Markarian 421

Markarian 421 was the first extragalactic source to be detected with high statistical certainty at TeV energies. The Whipple Observatory gamma-ray telescope has been used to observe the Active Galactic Nucleus, Markarian 421 in 1996 and 1997. The rapid variability observed in TeV gamma rays in previous years is confirmed. Doubling times as short as 15 minutes are reported with flux levels reaching 15 photons per minute. The TeV energy spectrum is derived using two independent methods. The implications for the intergalactic infra-red medium of an observed unbroken power law spectrum up to energies of 5 TeV is discussed.Comment: 4 pages, 4 figures, to appear in proceedings of 25 ICRC (Durban