1,663 research outputs found

    Determination of Equilibrium Constants for the Reaction between Acetone and HO_2 Using Infrared Kinetic Spectroscopy

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    The reaction between the hydroperoxy radical, HO_2, and acetone may play an important role in acetone removal and the budget of HO_x radicals in the upper troposphere. We measured the equilibrium constants of this reaction over the temperature range of 215–272 K at an overall pressure of 100 Torr using a flow tube apparatus and laser flash photolysis to produce HO_2. The HO_2 concentration was monitored as a function of time by near-IR diode laser wavelength modulation spectroscopy. The resulting [HO_2] decay curves in the presence of acetone are characterized by an immediate decrease in initial [HO_2] followed by subsequent decay. These curves are interpreted as a rapid (<100 μs) equilibrium reaction between acetone and the HO_2 radical that occurs on time scales faster than the time resolution of the apparatus, followed by subsequent reactions. This separation of time scales between the initial equilibrium and ensuing reactions enabled the determination of the equilibrium constant with values ranging from 4.0 × 10^(–16) to 7.7 × 10^(–1)8 cm^3 molecule^(–1) for T = 215–272 K. Thermodynamic parameters for the reaction determined from a second-law fit of our van’t Hoff plot were Δ_(r)H°_(245) = −35.4 ± 2.0 kJ mol^(–1) and Δ_(r)S°_(245) = −88.2 ± 8.5 J mol^(–1) K^(–1). Recent ab initio calculations predict that the reaction proceeds through a prereactive hydrogen-bonded molecular complex (HO_2–acetone) with subsequent isomerization to a hydroxy–peroxy radical, 2-hydroxyisopropylperoxy (2-HIPP). The calculations differ greatly in the energetics of the complex and the peroxy radical, as well as the transition state for isomerization, leading to significant differences in their predictions of the extent of this reaction at tropospheric temperatures. The current results are consistent with equilibrium formation of the hydrogen-bonded molecular complex on a short time scale (100 μs). Formation of the hydrogen-bonded complex will have a negligible impact on the atmosphere. However, the complex could subsequently isomerize to form the 2-HIPP radical on longer time scales. Further experimental studies are needed to assess the ultimate impact of the reaction of HO_2 and acetone on the atmosphere

    Dissipative and Dispersive Optomechanics in a Nanocavity Torque Sensor

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    Dissipative and dispersive optomechanical couplings are experimentally observed in a photonic crystal split-beam nanocavity optimized for detecting nanoscale sources of torque. Dissipative coupling of up to approximately 500500 MHz/nm and dispersive coupling of 22 GHz/nm enable measurements of sub-pg torsional and cantilever-like mechanical resonances with a thermally-limited torque detection sensitivity of 1.2×10−20N m/Hz\times 10^{-20} \text{N} \, \text{m}/\sqrt{\text{Hz}} in ambient conditions and 1.3×10−21N m/Hz\times 10^{-21} \text{N} \, \text{m}/\sqrt{\text{Hz}} in low vacuum. Interference between optomechanical coupling mechanisms is observed to enhance detection sensitivity and generate a mechanical-mode-dependent optomechanical wavelength response.Comment: 11 pages, 6 figure

    Sketch: Pen and touch recognition [Workshop summary]

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    A Composite Seyfert 2 X-ray Spectrum: Implications for the Origin of the Cosmic X-ray Background

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    We present a composite 1-10 keV Seyfert 2 X-ray spectrum, derived from ASCA observations of a distance-limited sample of nearby galaxies. All 29 observed objects were detected. Above ~3 keV, the composite spectrum is inverted, confirming that Seyfert 2 galaxies as a class have the spectral properties necessary to explain the flat shape of the cosmic X-ray background spectrum. Integrating the composite spectrum over redshift, we find that the total emission from Seyfert 2 galaxies, combined with the expected contribution from unabsorbed type 1 objects, provides an excellent match to the spectrum and intensity of the hard X-ray background. The principal uncertainty in this procedure is the cosmic evolution of the Seyfert 2 X-ray luminosity function. Separate composite spectra for objects in our sample with and without polarized broad optical emission lines are also presented.Comment: 11 pages (AASTeX), including 3 figures. Accepted for publication in ApJ Letter

    Assembly of Molybdenum/Titanium μ-Oxo Complexes via Radical Alkoxide C−O Cleavage

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    Three-coordinate Ti(NRAr)_3 [R = C(CD_3)_2(CH_3), Ar = C_6H_3Me_2] was prepared in 73% yield by sodium amalgam reduction of ClTi(NRAr)_3 and in 83% yield upon treatment of TiCl_3(THF)_3 with 3 equiv of Li(NRAr)(OEt_2) in the presence of TMEDA. Ti(^tBuNPh)_3 was prepared similarly in 75% yield by treatment of TiCl_3(THF)_3 with 3 equiv of Li(^tBuNPh)(OEt_2) in the presence of TMEDA. Reaction of Ti(NRAr)_3 with NMo(O^tBu)_3 in hydrocarbon solvents at −35 °C generates a thermally unstable intermediate formulated as (^tBuO)_3Mo[μ-N]Ti(NRAr)_3, which readily loses a tert-butyl radical and isomerizes at 25 °C. Kinetics of the latter process were obtained over the temperature range 20−60 °C; the process exhibits clean first-order behavior. The following activation parameters were obtained:  ΔH⧧ = 21.4 ± 0.2 kcal mol^(-1) and ΔS⧧ = −3.7 ± 0.6 cal mol^(-1) K^(-1). The oxo-bridged product (^tBuO)_2(N)Mo[μ-O]Ti(NRAr)_3 was isolated in 83% yield from this reaction. Full characterization of the latter diamagnetic complex included an X-ray crystal structure and an ^(15)N NMR study. Ti(NRAr)_3 (1 equiv) reacts further with (^tBuO)_2(N)Mo[μ-O]Ti(NRAr)_3 to generate a species formulated as a second paramagnetic nitrido-bridged intermediate, (^tBuO)_2Mo{[μ-O]Ti(NRAr)_3}{[μ-N]Ti(NRAr)_3}, which at 25 °C loses a tert-butyl radical and isomerizes to give the final product, (^tBuO)(N)Mo{[μ-O]Ti(NRAr)_3}_2, isolated as an orange powder in 91% yield. Characterization of the latter diamagnetic complex included an ^(15)N NMR study. Attempts to displace a third tert-butyl radical by treatment of (^tBuO)(N)Mo{[μ-O]Ti(NRAr)_3}_2 with Ti(NRAr)_3 led to no reaction. Treatment of (^tBuO)(N)Mo{[μ-O]Ti(NRAr)_3}_2 with neat methyl iodide led to the isolation of (MeO)(N)Mo{[μ-O]Ti(NRAr)_3}_2 in 51% yield; ^(13)C and nitrido-^(15)N derivatives of this species were prepared for spectroscopic characterization. O_2Mo{[μ-O]Ti(^tBuNPh)_3}_2 was prepared in 59% yield upon treatment of MoO_2(O^tBu)_2 with 2 equiv of Ti(^tBuNPh)_3 in benzene at 65 °C. Full characterization of O_2Mo{[μ-O]Ti(^tBuNPh)_3}_2 included a single-crystal X-ray diffraction study. Previously reported (^iPrO)_3V[μ-O]Ti(NRAr)_3 was oxidized with ferrocenium triflate to give TfOTi(NRAr)_3 and OV(O^iPr)_3. TfOTi(NRAr)_3 was prepared independently in 80% yield by treatment of Ti(NRAr)_3 with ferrocenium triflate. (^iPrO)_3V[μ-O]Ti(NRAr)_3 is stable in the presence of methyl iodide. ITi(NRAr)_3 was prepared independently by treatment of Ti(NRAr)_3 with the stoichiometric amount of iodine. Paramagnetic (^tBuO)_3V[μ-O]Ti(NRAr)_3 was prepared as orange-brown needles in 94% yield and was found to be thermally stable. The relatively robust μ-nitrido compound (Me_2N)_3Mo[μ-N]Ti(^tBuNPh)_3, which was prepared in 77% isolated yield, showed no decomposition when heated in benzene at 70 °C for 13 h

    Dependence of Galaxy Quenching on Halo Mass and Distance from its Centre

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    We study the dependence of star-formation quenching on galaxy mass and environment, in the SDSS (z~0.1) and the AEGIS (z~1). It is crucial that we define quenching by low star-formation rate rather than by red colour, given that one third of the red galaxies are star forming. We address stellar mass M*, halo mass Mh, density over the nearest N neighbours deltaN, and distance to the halo centre D. The fraction of quenched galaxies appears more strongly correlated with Mh at fixed M* than with M* at fixed Mh, while for satellites quenching also depends on D. We present the M*-Mh relation for centrals at z~1. At z~1, the dependence of quenching on M* at fixed Mh is somewhat more pronounced than at z~0, but the quenched fraction is low (10%) and the haloes are less massive. For satellites, M*-dependent quenching is noticeable at high D, suggesting a quenching dependence on sub-halo mass for recently captured satellites. At small D, where satellites likely fell in more than a few Gyr ago, quenching strongly depends on Mh, and not on M*. The Mh-dependence of quenching is consistent with theoretical wisdom where virial shock heating in massive haloes shuts down accretion and triggers ram-pressure stripping, causing quenching. The interpretation of deltaN is complicated by the fact that it depends on the number of observed group members compared to N, motivating the use of D as a better measure of local environment.Comment: 23 pages, 13 figures, accepted by MNRA

    The DEEP3 Galaxy Redshift Survey: The Impact of Environment on the Size Evolution of Massive Early-type Galaxies at Intermediate Redshift

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    Using data drawn from the DEEP2 and DEEP3 Galaxy Redshift Surveys, we investigate the relationship between the environment and the structure of galaxies residing on the red sequence at intermediate redshift. Within the massive (10 < log(M*/Msun) < 11) early-type population at 0.4 < z <1.2, we find a significant correlation between local galaxy overdensity (or environment) and galaxy size, such that early-type systems in higher-density regions tend to have larger effective radii (by ~0.5 kpc or 25% larger) than their counterparts of equal stellar mass and Sersic index in lower-density environments. This observed size-density relation is consistent with a model of galaxy formation in which the evolution of early-type systems at z < 2 is accelerated in high-density environments such as groups and clusters and in which dry, minor mergers (versus mechanisms such as quasar feedback) play a central role in the structural evolution of the massive, early-type galaxy population.Comment: 11 pages, 5 figures, 2 tables; resubmitted to MNRAS after addressing referee's comments (originally submitted to journal on August 16, 2011

    Isolation and Monitoring of Cleanroom-Associated Microbial Contaminates From Geological Collections

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    Microbial contamination is of particular interest to geological curation as many microorganisms can change mineral composition and produce compounds used as biosignatures used for the detection of life. Microbial cells can change the mineral composition of rocks through organic acid production and direct enzymatic oxidation/reduction of transition metals. Enzymatic oxidation of iron and manganese can occur at a rate several orders of magnitude faster than under abiotic conditions and produce highly reactive nanoparticle- sized oxides that can react and sorb other metals and organic compounds. Many fungi can also produce organic acids that dissolve and chelate mineral matrices chemically reducing and dissolving rock surfaces. Finally, several common soil-associated bacteria and fungi produce secondary metabolites that contain unusual amino acid analogs and non-ribosomal peptides containing both L- and D- chirality used in characterizing carbonaceous chondrites and the detection of extraterrestrial life

    The DEEP2 Galaxy Redshift Survey: The Voronoi-Delaunay Method Catalog of Galaxy Groups

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    We present a public catalog of galaxy groups constructed from the spectroscopic sample of galaxies in the fourth data release from the Deep Extragalactic Evolutionary Probe 2 (DEEP2) Galaxy Redshift Survey, including the Extended Groth Strip (EGS). The catalog contains 1165 groups with two or more members in the EGS over the redshift range 0 0.6 in the rest of DEEP2. Twenty-five percent of EGS galaxies and fourteen percent of high-z DEEP2 galaxies are assigned to galaxy groups. The groups were detected using the Voronoi-Delaunay method (VDM) after it has been optimized on mock DEEP2 catalogs following similar methods to those employed in Gerke et al. In the optimization effort, we have taken particular care to ensure that the mock catalogs resemble the data as closely as possible, and we have fine-tuned our methods separately on mocks constructed for the EGS and the rest of DEEP2. We have also probed the effect of the assumed cosmology on our inferred group-finding efficiency by performing our optimization on three different mock catalogs with different background cosmologies, finding large differences in the group-finding success we can achieve for these different mocks. Using the mock catalog whose background cosmology is most consistent with current data, we estimate that the DEEP2 group catalog is 72% complete and 61% pure (74% and 67% for the EGS) and that the group finder correctly classifies 70% of galaxies that truly belong to groups, with an additional 46% of interloper galaxies contaminating the catalog (66% and 43% for the EGS). We also confirm that the VDM catalog reconstructs the abundance of galaxy groups with velocity dispersions above ~300 km s^(–1) to an accuracy better than the sample variance, and this successful reconstruction is not strongly dependent on cosmology. This makes the DEEP2 group catalog a promising probe of the growth of cosmic structure that can potentially be used for cosmological tests
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