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At least 253 records · Page 14

Calculated rate constants for the reaction ClO + O yields Cl + O2 between 220 and 1000 deg K

Classical trajectory calculations are presented for the reaction ClO + O yields Cl + O2, a reaction which is an important step in the chlorine-catalyzed destruction of ozone which is thought to occur in the 220 and 1000 K. The calculated rate constant is 4.36 x 10 to the minus 11th power exp (-191/T)cu cm molecule (-1)s(-1) and its value at 300 K is 2.3 plus or minus 10 to the 11th power cu cm molecule (-1)s(-1), about a factor of 2 lower than recent experimental data. The empirical potential energy surface used in the calculations was constructed to fit experimental data for ClO, O2 and ClOO molecules. Other important features of this potential surface, such as the barrier to reaction, were varied systematically and calculations were performed for a range of conditions to determine the best theoretical rate constants. Results demonstrate the utility of classical trajectory methods for determining activation energies and other kinetic data for important atmospheric reactions.

Jaffee, R. L.↗

Rate constant for the reaction ClO + NO yields Cl + NO2

The rate constant for the reaction ClO + NO yields Cl + NO2 has been determined over the temperature range 226.7-415.4 K in a discharge flow system using a mass spectrometer as a detector. The results, expressed in the Arrhenius form, are compared with previous measurements.

Leu, M. T.↗

Cosmic-ray-produced Cl-36 and Mn-53 in Allan Hills-77 meteorites

Cosmic-ray-produced Mn-53 has been determined by neutron activation in nine Allan Hills-77 meteorites. Additionally, Cl-36 has been measured in seven of these objects using tandem accelerator mass spectrometry. These results, along with C-14 and Al-26 concentrations determined elsewhere, yield terrestrial ages ranging from 10,000 to 700,000 years. Weathering was not found to result in Mn-53 loss.

Nishiizumi, K.↗

Experimental SF6/-//SF6 and Cl/-//CFC13 electron-attachment cross sections in the energy range 0-200 meV

Experimental cross sections for the electron-attachment processes for SF6(-)/SF6 and Cl(-)/CFl3 are reported in the energy range 0-200 meV by normalizing each attachment line shape to measurement of a thermal rate coefficient. When the same ion states are detected, good agreement is found between present values, for which a monoenergetic electron source is used, and swarm-unfolded results. The present data constitute a new limit for cross sections reported at high resolution at the lowest electron energy.

Chutjian, A.↗

Calculation of SF6-/SF6 and Cl-/CFCl3 electron attachment cross sections in the energy range 0-100 meV

Electron attachment cross sections for the processes SF6-/SF6 and Cl-/CFCl3 are calculated in a local theory using a model in which diatomic-like potential energy curves for the normal modes are constructed from available spectroscopic data. Thermally populated vibrational and rotational levels are included. Good agreement is found with experimental cross sections in the energy range 5-100 meV for a particular choice of potential energy curve parameters.

Chutjian, A.↗

Kinetics of the reaction O + ClO yields Cl + O2

The bimolecular rate constant for the reaction O + ClO yields Cl + O2 has been measured over the temperature range 236-422 K in a discharge flow system using atomic oxygen resonance fluorescence at 130 nm to monitor the decay of O in an excess of ClO. The results are found to be independent of the method used to produce the ClO radical. At 296 K, the rate constant is given by (3.6 + or - 0.7) x 10 to the -11th cu cm/sec and the temperature dependence expressed in Arrhenius form by k2 = (5.0 + or - 1.0) x 10 to the -11th exp-(96 + or - 20)/T cu cm/sec. The results are compared with earlier values, and the implications for stratospheric chemistry are discussed briefly.

Leu, M.-T.↗

Kinetics of the reaction O + ClO yields Cl + O2

The kinetics of the reaction O + ClO yields Cl + O2 (k1) were studied by using resonance fluorescence to monitor the decay of O atoms which had been generated from the laser photolysis of ClO. A discharge flow system was used to generate the ClO and its concentration was measured directly by multipass absorption spectrometry. The results are k1(298) = (4.2 + or -0.8) x 10 to the -11th cu cm/s (including systematic errors) with E/R determined to lie in the range + or - 200 K. The literature data are reviewed and a composite value of k1(T) = 6.0 x 10 to the -11th exp-(100/T) is recommended for stratospheric modeling calculations. The atmospheric implications of the revised rate constant are discussed briefly.

Margitan, J. J.↗

Kinetics of the reaction Cl + NO2 + M

Using atomic chlorine resonance fluorescence at 140 nm to detect the decay of atomic chlorine in the presence of an excess of NO2, the rate constant for the reaction Cl + NO2 + M, where M is the total gas concentration, is measured over the temperature range 264 to 417 K and at a pressure 1 to 7 torr in a discharge flow system. The rate constants for M= He and M= N2 are measured and the results are summarized in a table. The systematic error of the rate constants is estimated to be about 15 percent. A static photolysis system coupled with an FTIR spectrophotometer is used to determine the branching ratio for the formation of two possible isomers. The ratio is concluded to be ClONO (greater than or equal 75 percent) and ClNO2 (less than or equal 25 percent) which is in agreement with the results of Niki et al. (1978).

Leu, M.-T.↗

The changes in small metal cluster size with adsorption Be13Xn, X = H, O, S, Cl and F

The Be-Be and Be-adsorbate distances are optimized for small Be13Xn clusters,s assuming only two independent degrees of freedom. Results for chemisorption into the three-fold hollows are quite similar to those found for small metal clusters on supports. It is predicted that Cl and F will have the same effect on the metal-metal bond lengths, and so will O and S.

Bauschlicher, C. W., Jr.↗

Cross sections for H(-) and Cl(-) production from HCl by dissociative electron attachment

A crossed target beam-electron beam collision geometry and a quadrupole mass spectrometer have been used to conduct dissociative electron attachment cross section measurements for the case of H(-) and Cl(-) production from HCl. The relative flow technique is used to determine the absolute values of cross sections. A tabulation is given of the attachment energies corresponding to various cross section maxima. Error sources contributing to total errors are also estimated.

Orient, O. J.↗

Coverage dependent effects on metal surfaces - O, S, F, and Cl on Ni

The c(2 x 2) and p(2 x 2) vibrational frequencies for a rigid Ni lattice are computed for O, S, F, and Cl on Ni(100). It is found that only O/Ni(100) shows a large difference in rigid lattice vibrational frequency. A large shift in rigid lattice vibrational frequency is also found for O/Ni(111) between 0.25 and 0.5 monolayer coverages. Also associated with the change in coverage, is a change in the height above the surface R(perpendicular). This varies from a 0.11 A reduction for O/Ni(100), to an expansion of 0.06 A for F/Ni(100).

Bauschlicher, C. W., Jr.↗

Three-color CCD photometry of the distant cluster of galaxies Cl 0024 + 1654

Photometry of 265 galaxies in rich cluster Cl 0024 + 1654 (z = 0.39), based on CCD imaging in three filters, is presented. The luminosity of this system ranks it among the richest known clusters, and it has a blue mass-to-light ratio of about 210. The color-magnitude diagram has a prominent E/S0 sequence. There are essentially no blue cluster members brighter than r equals about 19.3, and only very red galaxies inhabit the central 30 arcsec of the cluster. The blue cluster members have sizes and surface brightnesses similar to spiral galaxies in nearby clusters.

Schneider, D. P.↗

A flash spectrum of Cl I, C I, N I, and Ni II absorption in 31 Cygni: A direct observation of the reversing layer

In the process of surveying IUE observations of the zeta Aurigae binary system 31 Cygni for evidence of a shock, the presence of narrow low temperature lines Cl I, C I, N I, and Ni II has been discovered. These lines cannot be due to the local interstellar medium, since they appear only in one of the 16 high resolution, short wavelength observations made of this system. The phase of their appearance is theta = 0.017, approximately two months after egress of the blue dwarf component from eclipse behind the cool supergiant. Such lines might be produced by the shining of the hot dwarf companion's continuum through the edge of the supergiant's reversing layer or through a condensation in the supergiant atmosphere. If the former is the case, then the height of the reversing layer may be estimated from this observation. The radial velocities and equivalent widths of ten of these lines have been measured and the former is found to be -8.2 +/- 0.5 km/sec, precisely equal to the radial velocity of the system center of mass. This places a strict upper limit on the rotational velocity of the supergiant: V sub rot less than 2 km/s to better than 3 sigma.

Ahmad, Imad A.↗

Determination of O2(a1Delta g) and O2(b1Sigma + g) yields in the reaction O + ClO yields Cl + O2 - Implications for photochemistry in the atmosphere of Venus

A discharge flow apparatus with a chemiluminescence detector was used to investigate the reaction O + ClO yields Cl + O2(asterisk), where O2(asterisk) = O2(a1Delta g) or O2(b1Sigma + g). It is found that the observed O2(a1Delta g) airglow of Venus cannot be explained in the framework of standard photochemistry using the experimental results obtained here and those reported in the recent literature. The possibility of an alternative source of O atoms derived from SO2 photolysis in the Venus mesosphere is suggested.

Leu, Ming-Taun↗

Cl-rich minerals in Archean granulite facies ironstones from the Beartooth Mountains, Montana, USA: Implications for fluids involved in granulite metamorphism

The implications of Cl-rich minerals in granulite facies rocks are discussed. Results from ironstones of the Beartooth Mountains, Montana are discussed. It is suggested that CO2-brine immiscibility might be applicable to granulite facies conditions, and if so, then aqueous brines might be preferentially adsorbed onto mineral surfaces relative to CO2.

Henry, D. J.↗

Accurate oscillator strengths for interstellar ultraviolet lines of Cl I

Analyses on the abundance of interstellar chlorine rely on accurate oscillator strengths for ultraviolet transitions. Beam-foil spectroscopy was used to obtain f-values for the astrophysically important lines of Cl I at 1088, 1097, and 1347 A. In addition, the line at 1363 A was studied. Our f-values for 1088, 1097 A represent the first laboratory measurements for these lines; the values are f(1088)=0.081 +/- 0.007 (1 sigma) and f(1097) = 0.0088 +/- 0.0013 (1 sigma). These results resolve the issue regarding the relative strengths for 1088, 1097 A in favor of those suggested by astronomical measurements. For the other lines, our results of f(1347) = 0.153 +/- 0.011 (1 sigma) and f(1363) = 0.055 +/- 0.004 (1 sigma) are the most precisely measured values available. The f-values are somewhat greater than previous experimental and theoretical determinations.

Schectman, R. M.↗

Pressure broadening of the 2.5 THz H(Cl-35) rotational line by N2 and O2

The pressure broadening coefficients of the 2.5 THz rotation line of H(Cl-35) by N2 and O2, for application to the analysis of far infrared spectra obtained in the stratosphere, are reported. The broadening coefficients were measured in absorption at 296 and 201 L using a tunable far infrared spectrometer. Results show that at room temperature the N2 pressure broadening coefficient is 0.0669 +/-0.0021/cm/atm (2sigma), with a temperature coefficient B of 0.58 +/-0.02.

Park, K.↗

Morphology classification of galaxies in CL 0939+4713 using a ground-based telescope image

Morphological classification is studied for galaxies in cluster CL 0939+4712 at z = 0.407 using simple photometric parameters obtained from a ground-based telescope image with seeing of 1-2 arcseconds full width at half maximim (FWHM). By ploting the galaxies in a plane of the concentration parameter versus mean surface brightness, we find a good correlation between the location on the plane and galaxy colors, which are known to correlate with morphological types from a recent Hubble Space Telescope (HST) study. Using the present method, we expect a success rate of classification into early and late types of about 70% or possibly more.

Fukugita, M.↗