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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
NASA NTRS1981

Kinetics and mechanism of the disproportionation of BrO radicals

In the reported investigation, measurements were conducted of the rate constant for the reaction BrO + BrO yields products (1), taking into account the temperature range from 223 to 338 K and the pressure range from 50 to 475 torr of He. The flash photolysis-ultraviolet absorption technique was employed in the experiments. Two independent approaches were used to determine the relative rates of the two reaction branches, BrO + BrO yields BrOO + Br (1a), and BrO + BrO yields Br2 + O2 (1b), one dependent and the other independent of the BrO absorption cross section with the results being in excellent agreement. The rate constant, k(1), was found to be independent of pressure.

Sander, S. P.↗
NASA NTRS1981

The feasibility of using time-dependent photochemical calculations to infer radical species concentrations from solar occultation absorption measurements

In connection with fast chemical reactions, short-lived stratospheric species experience rapid concentration variations at sunset and sunrise. For solar occultation absorption measurements, these rapid concentration variations may introduce significant errors with respect to the inference of atmospheric abundances for some species due to asymmetrical concentration distributions. Most retrieval algorithms assume that concentration distributions are spherically symmetric. The effect of this assumption on the accuracy of inferred concentrations has been studied by Kerr et al. (1977). The present investigation considers the feasibility of using a time-dependent one-dimensional photochemical model to provide detailed information about the asymmetrical distribution for use in the retrieval procedure. As shown by Boughner et al. (1980), diurnal effects can be represented by an inhomogeneity factor. It is found that the NO retrieval improves considerably with the inclusion of a correction factor containing the asymmetrical variations.

Larsen, J. C.↗
NASA NTRS1983

Laboratory and astronomical measurement of the millimeter wave spectrum of the ethynyl radical CCH

The N = 0 yields 1 and 1 yields 2 rotational transitions of CCH at 87 and 174 GHz, respectively, have been detected in a laboratory glow discharge in a mixture of He and C2H2. The spectroscopic constants of CCH derived from measurements of the hfs of the transitions agree well with those derived from astronomical observations, confirming the astronomical detection of CCH. As the CCH lines in the Orion Nebula are narrower than the laboratory lines but less certain in rest frequency owing to uncertainty in the radial velocity, the most accurate values for the spectroscopic constants of CCH are obtained from a simultaneous fit of both the laboratory and astronomical data. For the rotation, centrifugal distortion, spin-rotation, and hyperfine constants, respectively, the values found are within 0.006 of 43674.534 MHz, within 0.0008 of 0.1071 MHz, within 0.004 of -62.606 MHz, b = within 0.019 MHz of 40.426, and c is within 0.026 of 12.254 MHz.

Gottlieb, C. A.↗
NASA NTRS1983

The microwave and far-infrared spectra of the CH radical

The frequencies, wavelengths, and line strengths for transitions of the CH molecule at microwave and far-infrared wavelengths have been calculated from an analysis of the laser magnetic resonance spectrum. The low-frequency transitions are between lambda-type doublets, while the higher frequency transitions are between different spin-rotation levels.

Brown, J. M.↗
NASA NTRS1983

Comments on laser-excited fluorescence of the hydroxyl radical: Relaxation coefficients at atmospheric pressure, appendix 5

The lifetime of the excited state of a atom or molecule is often determined from the rate of fluorescence decay originating as a function of buffer gas pressure, an accurate determination is made of the rates of collision induced transitions away from the excited state. Deconvolution can in principle be employed to resolve fluorescence times shorter than the response times of the system. However, attainable reproducibility and accuracy in actual experiments usually set a limit beyond which no meaningful results are expected. Prudence thus dictates that the results of deconvolution be viewed with extreme caution whenever fluorescence time much shorter than the response of times of the system are indicated.

Wang, C. C.↗
NASA NTRS1983

The photodissociation lifetimes of the OH and OD radicals in comets

The photodissociation rates of OH and OD molecules due to absorption of solar radiation in the X(2)Pi-A(2)Sigma(+) electronic transition are calculated to lie between 3.5 and 6.7 x 10 to the -6th/sec for OH for heliocentric velocities between -60 and +60 km/sec and at about 4.7 x 10 to the -7th/sec for OD at 1 AU from the sun. The corresponding lifetimes, which are upper bounds to the actual lifetimes, are generally consistent with the observational cometary data.

Singh, P. D.↗
NASA NTRS1984

Infrared and far-infrared transition frequencies for the CH2 radical

A list of frequencies and intensities for transitions of CH2 in the middle and far infrared regions is presented which should aid in the detection of CH2 and provide valuable information on the local physical and chemical environment. Results are presented for frequency, vacuum wavelength, and line strength for rotational transition frequencies and for the transition frequencies of the v(2) band.

Sears, T. J.↗
NASA NTRS1984

A measurement of the vibrational band strength for the v3 band of the HO2 radical

Laboratory measurements of the v(3) band strength of HO2 using a tunable diode laser to measure the absorption strength of a vibration-rotation line in the P branch near 1080/cm are reported. The HO2 is generated in a discharge-flow system by reaction of fluorine atoms with excess H2O2: F + H2O2 - HO2 + HF. The HO2 concentration is determined from measurements of F-atom concentrations using both chemical titration with Cl2 and tunable diode laser absorption by the F-atom spin-orbit transition near 404/cm. The experimental data are consistent with a value of k(3) = (1.6 + or - 0.3) x 10 to the 12th cu cm/s and a ratio k(4)/k(1) = 1.0 + or - 0.4. The line strength for the 6(15) - 7(16)F(1) transition is 2.9 x 10 to the -21 sq cm/molecule/cm, which corresponds to a v(3) band strength of 35 + or - 9/sq cm/(STP atm). This value is a factor of 1.6 to 6 lower than previous ab initio calculations.

Zahniser, M. S.↗
NASA NTRS1984

Mechanism of the atmospheric oxidation of sulfur dioxide - Catalysis by hydroxyl radicals

A flash photolysis/resonance fluorescence technique was used to investigate the decay of OH due to the reaction OH + SO2 (+M) to HOSO2 (+M). In the presence of small amounts of NO (10 to the 14th per cu cm), the decays deviated from the normal semilogarithmic linearity due to reformation of OH. On the basis of computer simulations of the decay curves, it is suggested that the reactions HOSO2 + O2 to HO2 + SO3 (k3), and HO2 + HO to OH + NO2 are the likely subsequent steps in SO2 oxidation. The upper limit for the binding energy of HOSO2 relative to OH + SO2 is estimated to be 32 kcal/mol. The atmospheric implications of a catalytic oxidation mechanism are briefly discussed.

Margitan, J. J.↗
NASA NTRS1985

The microwave and far-infrared spectra of the SiH radical

Consideration of Si's cosmic abundance leads to the expectation that the related molecule SiH may be detected in extraterrestrial sources. A tabulation is presented of frequencies, wavelengths, and line strengths for SiH molecule transitions at microwave and far-IR wavelengths, on the basis of an analysis of its laser magnetic resonance spectrum. It is hoped that the frequencies presented will be useful to both laboratory spectroscopists and astrophysicists.

Brown, J. M.↗
NASA NTRS1985

Laboratory and astronomical detection of the deuterated ethynyl radical CCD

Two rotational transitions of CCD, N = 1-2 at 144 GHz and 2-3 at 216 GHz, were detected in a laboratory glow discharge through deuterated acetylene and helium, after which one, N = 2-1, was detected toward the rich molecular cloud behind the Orion Nebula. The 144 GHz transition is a well-resolved spin doublet split by 55 MHz, the components of which contain hyperfine structure of the order of 1 MHz, so far only partially resolved. From observations toward two positions in Orion, at and near the Kleinmann-Low nebula, the column density of CCD is determined to be 1.8 x 10 to the 13th/sq cm and the isotopic ratio CCD/CCH = 0.05. CCD was not detected at two positions in TMC-1.

Vrtilek, J. M.↗
NASA NTRS1986

UV laser deposition of metal films by photogenerated free radicals

A novel photochemical method for liquid-phase deposition of metal films is described. In the liquid phase deposition scheme, a metal containing compound and a metal-metal bonded carbonyl complex are dissolved together in a polar solvent and the mixture is irradiated using a UV laser. The optical arrangement consists of a HeCd laser which provides 7 mW of power at a wavelength of 325 nm in the TEM(OO) mode. The beam is attenuated and may be expanded to a diameter of 5-20 mm. Experiments with photochemical deposition of silver films onto glass and quartz substrates are described in detail. Mass spectrometric analysis of deposited silver films indicated a deposition rate of about 1 A/s at incident power levels of 0.01 W/sq cm. UV laser-induced copper and palladium films have also been obtained. A black and white photograph showing the silver Van Der Pauw pattern of a solution-deposited film is provided.

Montgomery, R. K.↗
NASA NTRS1986

OH radical measurements by optical absorption spectroscopy

The long path absorption spectroscopy (LPA) measurement of OH utilizes the strong UV absorption spectrum of the molecule with well resolved rotational lines around 308 nm. The light source consists of an Ar ion laser pumped CW dye laser, the output of which is frequency doubled to emit a spectrally smooth light profile of 0.1 nm FWHM at 308 nm. This is considerably broader than the sharp (0.0018 nm wide) absorption features of OH and also wider than the total spectral region (0.06 nm) scanned around the OH lines. For field measurements a Cassegrain-type telescope expands the small diameter of the original laser beam by a factor of 50 to about a 0.25-m diameter in order to reduce the divergence of the beam as well as its mean photon flux density, thus reducing the maximum self-generated OH concentration to 40,000 cu. cm. The light is passed into the open atmosphere and reflected at about 5 km distance resulting in a 10-km light path length. A telescope focuses the returning light onto the entrance slit of a monochromator the single exit slit of which is replaced by a mechanical scanning device operating at a scan repetition rate of 6.6 KHz. For a typical measurement (1h duration) some 20,000,000 scans are averaged, rendering the contribution of atmospheric turbulence to the spectral noise negligible.

Platt, U.↗