Heptacarbonyldiosmium and Hexacarbonyldiosmium: Two Highly Unsaturated Binuclear Osmium Carbonyls

A total of nine singlet structures for Os2(CO)7 and 15 structures (nine singlet and six triplet) for Os2(CO)6 have been found by density functional theory thereby indicating very complicated energy surfaces. The global minimum for Os2(CO)7 is a doubly carbonyl bridged structure Os2(CO)5(μ-CO)2 with an Os=Os distance of 2.67 Å suggesting a formal double bond and hence a 16-electron rather than an 18-electron configuration for one of the osmium atoms. However, at only slightly higher energy (3.2 kcal mol−1) lies an unbridged Os2(CO)7 structure with a shorter Os≡Os distance of 2.54 Å, corresponding to a formal triple bond and an 18-electron configuration for each osmium atom. The global minimum for Os2(CO)6 can be derived from that of Os2(CO)7 by removal of a carbonyl group while retaining the Os=Os double bond and the two bridging carbonyl groups. Slightly higher energy Os2(CO)6 structures at ≈3 kcal mol−1 or more above the global minimum have short Os-Os quadrupole bond distances around 2.4 Å, consistent with the formal quadruple bonds necessary to give both osmium atoms the favored 18-electron configuration. None of the 24 structures for Os2(CO)7 and Os2(CO)6 found in this work has a four-electron donor η2-μ-CO bridging carbonyl group

Can Light Echoes Account for the Slow Decay of Type IIn Supernovae?

The spectra of type IIn supernovae indicate the presence of apre-existing slow, dense circumstellar wind (CSW). If the CSW extends sufficiently far from the progenitor star, then dust formation should occur in the wind. The light from the supernova explosion will scatter off this dust and produce a light echo. Continuum emission seen after the peak will have contributions from both this echo as well as from the shock of the ejecta colliding with the CSW, with a fundamental question of which source dominates the continuum. We calculate the brightness of the light echo as a function of time for a range of dust shell geometries, and use our calculations to fit to the light curves of SN 1988Z and SN 1997ab, the two slowest declining IIn supernovae on record. We find that the light curves of both objects can be reproduced by the echo model. However, their rate of decay from peak, color at peak and their observed peak absolute magnitudes when considered together are inconsistent with the echo model. Furthermore, when the observed values of M$_{B}$ are corrected for the effects of dust scattering, the values obtained imply that these supernovae have unrealistically high luminosities. We conclude that light echoes cannot properly account for the slow decline seen in some IIn's, and that the shock interaction is likely to dominate the continuum emission.Comment: 15 pages, 9 figure

Causes and Consequences of Broad-Scale Changes in the Distribution of Migratory Caribou (Rangifer tarandus) of Southern Hudson Bay

Understanding the factors driving changes in species distributions is fundamental to conservation, but for wide-ranging species this is often complicated by the need for broad-scale observations across space and time. In the last three decades, the location of summer concentrations of migratory caribou (Rangifer tarandus) in southern Hudson Bay (SHB), Canada, has shifted south and east as much as 500 km. We used long-term data (1987 – 2011) to test two hypotheses that could explain the distribution shift: forage depletion and anthropogenic disturbance. Over time and space, we compared the body size of live-captured adult female caribou, dietary quality from fecal nitrogen in July, the location of VHF- and GPS-collared female caribou in July, distribution of all-terrain vehicle (ATV) tracks and caribou tracks in August, and the proximity of collared caribou to sections of the coast with higher ATV activity in spring and summer. The forage depletion hypothesis was supported by greater body size and dietary quality in caribou of the eastern portion of SHB than in western SHB animals in 2009 – 11. The anthropogenic disturbance hypothesis was supported by the negative correlation of the distributions of ATV tracks and caribou tracks on the coast in 2010 and the fact that caribou avoided areas with ATV activity by 10 – 14 km. In 1987, collared caribou were observed largely along the coast in western SHB in mid-July, while in 2009 – 11, they were inland in western SHB and along the coast in eastern SHB. While these locations demonstrate a substantial change in summer distri­bution over three decades, we were unable to differentiate between forage depletion and anthropogenic disturbance as a single causal factor of the distribution shift.La compréhension des facteurs qui influencent les changements caractérisant les distributions des espèces est fondamentale aux efforts de conservation, mais pour les espèces dont l’aire de distribution est étendue, ce principe est souvent compliqué par la nécessité de faire des observations à grande échelle, dans le temps et dans l’espace. Au cours des trois dernières décennies, l’emplacement des concentrations estivales du caribou migrateur (Rangifer tarandus) dans le sud de la baie d’Hudson (SBH), au Canada, s’est déplacé vers le sud et vers l’est dans une mesure de 500 km. Nous nous sommes appuyés sur des données de longue haleine (1987–2011) pour mettre à l’épreuve deux hypothèses susceptibles d’expliquer ce changement en matière de distribution, soit l’appauvrissement du fourrage et la perturbation anthropique. Au fil du temps et de l’espace, nous avons comparé la taille du corps des caribous femelles adultes capturées vivantes, la qualité de leur alimentation à partir de l’azote fécal en juillet, l’emplacement des femelles portant un collier de type VHF ou GPS en juillet, la répartition des traces de véhicules tout terrain (VTT) et des pistes de caribou en août de même que la proximité des caribous portant un collier aux tronçons de la côte où la présence de VTT est plus grande au printemps et à l’été. L’hypothèse de l’appauvrissement du fourrage a été étayée par la plus grande taille du corps et la qualité de l’alimentation du caribou de la zone est du SBH comparativement à celles du caribou de l’ouest du SBH entre 2009 et 2011. Pour sa part, l’hypothèse perturbation anthropique a été appuyée par la corrélation négative caractérisant la répartition des pistes de VTT et des traces de caribou sur la côte en 2010 et par le fait que les caribous sont restés à l’écart des zones fréquentées par les VTT dans une mesure de 10 à 14 km. En 1987, des caribous portant un collier ont été observés en grand nombre le long de la côte ouest du SBH à la mi-juillet, tandis que de 2009 à 2011, ils ont été repérés à l’intérieur des terres dans l’ouest du SBH et le long de la côte est du SBH. Bien que ces emplacements indiquent un important changement en matière de distribution estivale au cours de trois décennies, nous n’avons pas été en mesure de faire une distinction entre l’appauvrissement du fourrage et la perturbation anthropique en tant que facteur causal unique du changement de distribution

Petrogenesis of Lava from Christmas Island, Northeast Indian Ocean: Implications for the Nature of Recycled Components in Non-Plume Intraplate Settings

Lava samples from the Christmas Island Seamount Province (CHRISP) record an extreme range in enriched mantle (EM) type Sr-Nd-Pb-Hf isotope signatures. Here we report osmium isotope data obtained on four samples from the youngest, Pliocene petit-spot phase (Upper Volcanic Series, UVS; ~4.4 Ma), and four samples from the earlier, Eocene (Lower Volcanic Series, LVS; ~40 Ma) shield building phase of Christmas Island. Osmium concentrations are low (5–82 ppt) with initial Os isotopic values (187Os/188Osi) ranging from (0.1230–0.1679). Along with additional new geochemical data (major and trace elements, Sr-Nd-Pb isotopes, olivine δ18O values), we demonstrate the following: (1) The UVS is consistent with melting of shallow Indian mid-ocean ridge basalt (MORB) mantle enriched with both lower continental crust (LCC) and subcontinental lithospheric mantle (SCLM) components; and (2) The LVS is consistent with recycling of SCLM components related to Gondwana break-up. The SCLM component has FOZO or HIMU like characteristics. One of the LVS samples has less radiogenic Os (γOs –3.4) and provides evidence for the presence of ancient SCLM in the source. The geochemistry of the Christmas Island lava series supports the idea that continental breakup causes shallow recycling of lithospheric and lower crustal components into the ambient MORB mantle

The Early Optical Afterglow of GRB 030418 and Progenitor Mass Loss

The ROTSE-IIIa telescope and the SSO 40 inch (1.0 m) telescope, both located at Siding Spring Observatory, imaged the early-time afterglow of GRB 030418. In this report, we present observations of the early afterglow, first detected by the ROTSE-IIIa telescope 211 s after the start of the burst and only 76 s after the end of the gamma-ray activity. We detect optical emission that rises for ∼600 s, slowly varies around R = 17.3 mag for ∼1400 s, and then fades as a power law of index α = -1.36. Additionally, the ROTSE-IIIb telescope, located at McDonald Observatory, imaged the early-time afterglow of GRB 030723. The behavior of this light curve was qualitatively similar to that of GRB 030418, but 2 mag dimmer. These two afterglows are dissimilar to other afterglows such as GRB 990123 and GRB 021211. We investigate whether or not the early afterglow can be attributed to a synchrotron break in a cooling synchrotron spectrum as it passes through the optical band, but we find that this model is unable to accurately describe the early light curve. We present a simple model for gamma-ray burst emission emerging from a wind medium surrounding a massive progenitor star. This model provides an effective description of the data and suggests that the rise of the afterglow can be ascribed to extinction in the local circumburst environment. In this interpretation, these events provide further evidence of the connection between gamma-ray bursts and the collapse of massive stars.This work has been supported by NASA grants NAG5- 5281 and F006794, NSF grants AST 01-19685 and 01-05221, the Australian Research Council, the University of New South Wales, and the University of Michigan. Work performed at LANL is supported by NASA SR&T through Department of Energy (DOE) contract W-7405-ENG-36 and through internal LDRD funding

Solubility of Rock in Steam Atmospheres of Planets

Extensive experimental studies show that all major rock-forming elements (e.g., Si, Mg, Fe, Ca, Al, Na, K) dissolve in steam to a greater or lesser extent. We use these results to compute chemical equilibrium abundances of rocky-element-bearing gases in steam atmospheres equilibrated with silicate magma oceans. Rocky elements partition into steam atmospheres as volatile hydroxide gases (e.g., Si(OH)4, Mg(OH)2, Fe(OH)2, Ni(OH)2, Al(OH)3, Ca(OH)2, NaOH, KOH) and via reaction with HF and HCl as volatile halide gases (e.g., NaCl, KCl, CaFOH, CaClOH, FAl(OH)2) in much larger amounts than expected from their vapor pressures over volatile-free solid or molten rock at high temperatures expected for steam atmospheres on the early Earth and hot rocky exoplanets. We quantitatively compute the extent of fractional vaporization by defining gas/magma distribution coefficients and show that Earth's subsolar Si/Mg ratio may be due to loss of a primordial steam atmosphere. We conclude that hot rocky exoplanets that are undergoing or have undergone escape of steam-bearing atmospheres may experience fractional vaporization and loss of Si, Mg, Fe, Ni, Al, Ca, Na, and K. This loss can modify their bulk composition, density, heat balance, and interior structure

Regularity Properties and Pathologies of Position-Space Renormalization-Group Transformations

We reconsider the conceptual foundations of the renormalization-group (RG) formalism, and prove some rigorous theorems on the regularity properties and possible pathologies of the RG map. Regarding regularity, we show that the RG map, defined on a suitable space of interactions (= formal Hamiltonians), is always single-valued and Lipschitz continuous on its domain of definition. This rules out a recently proposed scenario for the RG description of first-order phase transitions. On the pathological side, we make rigorous some arguments of Griffiths, Pearce and Israel, and prove in several cases that the renormalized measure is not a Gibbs measure for any reasonable interaction. This means that the RG map is ill-defined, and that the conventional RG description of first-order phase transitions is not universally valid. For decimation or Kadanoff transformations applied to the Ising model in dimension $d \ge 3$, these pathologies occur in a full neighborhood $\{ \beta > \beta_0 ,\, |h| < \epsilon(\beta) \}$ of the low-temperature part of the first-order phase-transition surface. For block-averaging transformations applied to the Ising model in dimension $d \ge 2$, the pathologies occur at low temperatures for arbitrary magnetic-field strength. Pathologies may also occur in the critical region for Ising models in dimension $d \ge 4$. We discuss in detail the distinction between Gibbsian and non-Gibbsian measures, and give a rather complete catalogue of the known examples. Finally, we discuss the heuristic and numerical evidence on RG pathologies in the light of our rigorous theorems.Comment: 273 pages including 14 figures, Postscript, See also ftp.scri.fsu.edu:hep-lat/papers/9210/9210032.ps.