8,229 research outputs found

    Infrared spectra of the cluster ions H7O<sup> + </sup><sub>3</sub>·H2 and H9O<sup> + </sup><sub>4</sub>·H2

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    Infrared spectra of hydrated hydronium ions weakly bound to an H2 molecule, specifically H7O + 3 ·H2 and H9O + 4 ·H2, have been observed. Mass-selected parent ions, trapped in a radio frequency ion trap, are excited by a tunable infrared laser; following absorption, the complex predissociates with loss of the H2, and the resulting fragment ions are detected. Spectra have been taken from 3000 to 4000 cm^−1, with a resolution of 1.2 cm^−1. They are compared to recent theoretical and experimental spectra of the hydronium ion hydrates alone. Binding an H2 molecule to these clusters should only weakly perturb their vibrations; if so, our spectra should be similar to spectra of the hydrated hydronium ions H7O + 3 and H9O + 4

    Near-Infrared Kinetic Spectroscopy of the HO_2 and C_2H_5O_2 Self-Reactions and Cross Reactions

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    The self-reactions and cross reactions of the peroxy radicals HO_2 and C_2H_5O_2 and HO_2 were monitored using simultaneous independent spectroscopic probes to observe each radical species. Wavelength modulation (WM) near-infrared (NIR) spectroscopy was used to detect HO_2, and UV absorption monitored HO_2 and C_2H_5O_2. The temperature dependences of these reactions were investigated over a range of interest to tropospheric chemistry, 221−296 K. The Arrhenius expression determined for the cross reaction, k_2(T) = (6.01^(+1.95)_(−1.47)) × 10^(−13) exp((638 ± 73)/T) cm^3 molecules^(−1) s^(−1) is in agreement with other work from the literature. The measurements of the HO_2 self-reaction agreed with previous work from this lab and were not further refined.(1) The C_2H_5O_2 self-reaction is complicated by secondary production of HO_2. This experiment performed the first direct measurement of the self-reaction rate constant, as well as the branching fraction to the radical channel, in part by measurement of the secondary HO_2. The Arrhenius expression for the self-reaction rate constant is k_3(T) = (1.29^(+0.34)_(−0.27)) × 10^(−13)exp((−23 ± 61)/T) cm^3 molecules^(−1) s^(−1), and the branching fraction value is α = 0.28 ± 0.06, independent of temperature. These values are in disagreement with previous measurements based on end product studies of the branching fraction. The results suggest that better characterization of the products from RO_2 self-reactions are required

    Evolution of Massive Black Hole Binaries

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    We present the result of large-scale N-body simulations of the stellar-dynamical evolution of a massive black-hole binary at the center of a spherical galaxy. We focus on the dependence of the hardening rate on the relaxation timescale of the parent galaxy. A simple theoretical argument predicts that a binary black hole creates the ``loss cone'' around it. Once the loss cone is formed, the hardening rate is determined by the rate at which field stars diffuse into the loss cone. Therefore the hardening timescale becomes proportional to the relaxation timescale. Recent N-body simulations, however, have failed to confirm this theory and various explanations have been proposed. By performing simulations with sufficiently large N (up to 10610^6) for sufficiently long time, we found that the hardening rate does depend on N. Our result is consistent with the simple theoretical prediction that the hardening timescale is proportional to the relaxation timescale. This dependence implies that most massive black hole binaries are unlikely to merge within the Hubble time through interaction with field stars and gravitational wave radiation alone.Comment: Reviced version accepted for publication in ApJ. Scheduled to appear in the February 10, 2004 issu

    BRST invariant Lagrangian of spontaneously broken gauge theories in noncommutative geometry

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    The quantization of spontaneously broken gauge theories in noncommutative geometry(NCG) has been sought for some time, because quantization is crucial for making the NCG approach a reliable and physically acceptable theory. Lee, Hwang and Ne'eman recently succeeded in realizing the BRST quantization of gauge theories in NCG in the matrix derivative approach proposed by Coquereaux et al. The present author has proposed a characteristic formulation to reconstruct a gauge theory in NCG on the discrete space M4×ZNM_4\times Z_{_N}. Since this formulation is a generalization of the differential geometry on the ordinary manifold to that on the discrete manifold, it is more familiar than other approaches. In this paper, we show that within our formulation we can obtain the BRST invariant Lagrangian in the same way as Lee, Hwang and Ne'eman and apply it to the SU(2)×\timesU(1) gauge theory.Comment: RevTeX, page

    TRW materials compatibility study with ethylene oxide/Freon 12 decontamination processes

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    Organic materials compatibility with ethylene oxide and Freon decontamination processe

    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

    Laboratory measurements and theoretical calculations of O_2 A band electric quadrupole transitions

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    Frequency-stabilized cavity ring-down spectroscopy was utilized to measure electric quadrupole transitions within the ^(16)O_2 A band, b^1Σ^+_g ← X^3Σ^-_g(0,0). We report quantitative measurements (relative uncertainties in intensity measurements from 4.4% to 11%) of nine ultraweak transitions in the ^NO, ^PO, ^RS, and ^TS branches with line intensities ranging from 3×10^(−30) to 2×10^(−29) cm molec.^(−1). A thorough discussion of relevant noise sources and uncertainties in this experiment and other cw-cavity ring-down spectrometers is given. For short-term averaging (t<100 s), we estimate a noise-equivalent absorption of 2.5×10^(−10) cm^(−1) Hz^(−1/2). The detection limit was reduced further by co-adding up to 100 spectra to yield a minimum detectable absorption coefficient equal to 1.8×10^(−11) cm^(−1), corresponding to a line intensity of ~2.5×10^(−31) cm molec.^(−1). We discuss calculations of electric quadrupole line positions based on a simultaneous fit of the ground and upper electronic state energies which have uncertainties <3 MHz, and we present calculations of electric quadrupole matrix elements and line intensities. The electric quadrupole line intensity calculations and measurements agreed on average to 5%, which is comparable to our average experimental uncertainty. The calculated electric quadrupole band intensity was 1.8(1)×10^(−27) cm molec.−1 which is equal to only ~8×10^(−6) of the magnetic dipole band intensity
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