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At least 343 records · Page 19

Laboratory detection of the C5H radical

The new linear molecule reported by Cernicharo et al. (1986) has been found in the same laboratory discharge in which C3H is observed, establishing conclusively that the molecule is C5H in its 2Pi ground state. Six rotational transitions in the 2Pi(1/2) ladder and four in the 2Pi(3/2), each split by lambda doubling, were observed. The twenty millimeter-wave lines were simultaneously fit by a standard Hamiltonian with five free parameters: the fine-structure constant, the rotational constant, the centrifugal distortion constant, and two lambda-doubling constants.

Gottlieb, C. A.↗

Production of Cl2O2 from the self-reaction of the ClO radical

The species Cl2O2 has been generated in a gaseous flow system at 220-240 K by reacting Cl atoms with one of three different ClO precursors: O3, Cl2O, or OClO. The infrared spectra of the reactive mixture indicate that at least two different dimers are produced: a predominant form with bands centered at 1225 and 1057/cm attributed to ClOOCl, and a second form with a band at 650/cm attributed to ClOClO. The UV spectrum of the predominant form shows a maximum absorption cross section of about 6.5 x 10 to the -18th sq cm/molecule around 270 nm, with a wing extending beyond 300 nm. The implications of these results for the chemistry of the stratosphere are discussed.

Molina, L. T.↗

Sources of cometary radicals and their jets - Gases or grains

The photosputtering of cometary CHON grains by solar UV radiation may furnish an inner coma source for the C atoms and C(+) ions observed in Comet Halley. A quantitative analysis is presented which constrains the size and/or morphology of the grains, together with a calculation giving attention to the dispersion of a trace gas jet in the cometary coma. Due to the large outflow speed and low temperature of the inner coma, a localized spatial region enriched in a trace parent gas will propagate radially outward while simultaneously diffusing and expanding, thereby preserving a jetlike appearance.

Combi, Michael R.↗

Concepts for radically increasing the numerical convergence rate of the Euler equations

Integral equation and finite difference methods have been developed for solving transonic flow problems using linearized forms of the transonic small disturbance and Euler equations. A key element is the use of a strained coordinate system in which the shock remains fixed. Additional criteria are developed to determine the free parameters in the coordinate straining; these free parameters are functions of the shock location. An integral equation analysis showed that the shock is located by ensuring that no expansion shocks exist in the solution. The expansion shock appears as oscillations in the solution near the sonic line, and the correct shock location is determined by removing these oscillations. A second objective was to study the ability of the Euler equation to model separated flow.

Nixon, David↗

The spectroscopic observation of the CH radical in its a4Sigma(-) state

The first spectroscopic observation of CH in the a 4Sigma(0-) state are reported. The molecule was generated in a discharge-flow system in the reaction betweeen fluorine atoms and methane or between oxygen atoms and acetylene at a total pressure of about 1 Torr. Several resonances associated with the N = 1 - 0 transitions of 4Sigma(-) CH were observed at three separate laser wavelengths, while those for the N = 2 - 1 transition were observed at two wavelengths. Each observed Zeeman component consists of a well-split doublet arising from proton hyperfine structure. The reasons for assigning the observations to CH in its a 4Sigma(-) state are discussed.

Nelis, Thomas↗

Absolute infrared band strength measurement of the ClO radical by Fourier transform infrared spectroscopy

High-resolution (0.005/cm) FTIR spectra of the X2Pi(i)-X2Pi(i) (1-0) rovibrational bands of (C-35)(O-16) and (Cl-37)(O-16) were obtained in 1 torr of helium carrier gas. After measuring the strengths of approximately 830 individual IR lines from several spectra, a total band strength of 13.1 + or - 1.1/sq cm atm and a first Herman-Wallis coefficient of (4.12 + or - 0.62) x 10 to the -3rd were determined.

Lang, Valerie I.↗

Branching ratios in the N + CH3 reaction - Formation of the methylene amidogen (H2CN) radical

The discharge-flow mass spectrometer system described by Brunning and Stief (1986) and Nejad et al. (1988) is used to determine the branching ratios for the reaction N + CH3. The results are presented in extensive tables and graphs and characterized in detail, and the implications for HCN formation in the atmosphere of Titan are considered. It is found that the main reaction channel at room temperature is H2CN + H, with about 10 percent giving HCN + H2; no isotope effects are seen when CH3 is replaced with CD3, and the branching ratios appear to be temperature-independent.

Marston, G.↗

Ozone destruction by chlorine radicals within the Antarctic vortex - The spatial and temporal evolution of ClO-O3 anticorrelation based on in situ ER-2 data

The chemical evolution of the Antarctic vortex region was studied during August 23-September 22, 1987 on the basis of in situ O3 and ClO data collected by the ER-2 aircraft. Particular attention is given to the evolution of the ClO-O3 anticorrelation from the first flight on August 23, 1987, which penetrated well into the vortex, through the course of 10 flights culminating on September 22, 1987. It is concluded that the disappearance of ozone within the Antarctic vortex results from halogen-catalyzed recombination of O3 to molecular oxygen.

Anderson, J. G.↗

Saturated fluorescence measurements of the hydroxyl radical in laminar high-pressure flames

The efficacy of laser saturated fluorescence (LSF) for OH concentration measurements in high pressure flames was studied theoretically and experimentally. Using a numerical model describing the interaction of hydroxyl with nonuniform laser excitation, the effect of pressure on the validity of the balanced cross-rate model was studied along with the sensitivity of the depopulation of the laser-coupled levels to the ratio of rate coefficients describing: (1) electronic quenching to (sup 2) Sigma (+) (v double prime greater than 0), and (2) vibrational relaxation from v double prime greater than 0 to v double prime = 0. At sufficiently high pressures and near-saturated conditions, the total population of the laser-coupled levels reaches an asymptotic value, which is insensitive to the degree of saturation. When the ratio of electronic quenching to vibrational relaxation is small and the rate of coefficients for rotational transfer in the ground and excited electronic states are nearly the same, the balanced cross-rate model remains a good approximation for all pressures. When the above ratio is large, depopulation of the laser-coupled levels becomes significant at high pressures, and thus the balanced cross-rate model no longer holds. Under these conditions, however, knowledge of the depletion of the laser-coupled levels can be used to correct the model. A combustion facility for operation up to 20 atm was developed to allow LSF measurements of OH in high pressure flames. Using this facility, partial saturation in laminar high pressure (less than or equal to 12.3 atm) C2H6/O2/N2 flames was achieved. To evaluate the limits of the balanced cross-rate model, absorption and calibrated LSF measurements at 3.1 and 6.1 atm were compared. The fluorescence voltages were calibrated with absorption measurements in an atmospheric flame and corrected for their finite sensitivity to quenching with: (1) estimated quenching rate coefficients, and (2) an in situ measurement from a technique employing two fluorescence detection geometries.

Carter, Campbell D.↗

The heat of formation of CN radicals and radiative lifetimes of the A 1 Sigma - state of C2N2

Radiative lifetimes have been measured for the stable vibrational levels of the A 1 sigma - electronic state of C2N2. They range from 1.3 microsec for the 4(sub 0)(sup 1) level to 0.66 microsec for the 1(sub 0)(sup 1) 4(sub 0)(sup 1) level and in general decrease with increasing vibrational excitation. Self-quenching rate constants range from gas kinetic to ten times that. Foreign gas quenching rates are slower. Observation of emission from the 1(sub 0)(sup 1) 4(sub 0)(sup 1) level sets a lower limit for the heat of formation of CN of 439.11 kJ/mol.

Barts, Samuel A.↗

Development of a two photon/laser induced fluorescence technique for the detection of atmospheric OH radicals

The development of a new mid-IR laser source was the primary goal. Backward propagating stimulated D2 Raman frequency down conversion of a commercially available 1.06 micron Nd:YAG laser was shown to generate an efficient source of 1.56 micron radiation with near diffraction limited beam quality. The efficient generation of a 2.9 micron laser source was also achieved using backward propagating CH4 Raman frequency down conversion of the 1.56 micron pump. Slightly higher efficiencies were obtained for frequency down conversion of the 1.06 micron Nd:YAG using the H2 Raman shift yielding a near diffraction limited source in the 200 mJ range at 1.9 micron. Similar conversion efficiencies are anticipated as a result of extending the wavelength coverage of recently available Ti:sapphire pulse laser to not only cover the 740 to 860 nm fundamental wavelength range but also the .95 to 1.15 and 1.06 to 1.33 micron range using D2 and H2, respectively. The anticipated sensitivity of a TP-LIF OH sensor using this mid-IR source would give signal limited detection of 1.4 x 10(exp 5) OH/cu cm under boundary layer conditions and 5.5 x 10(exp 4) OH/cu cm under free troposphere sampling conditions for a five minute signal integration period. This level of performance coupled with the techniques non-perturbing nature and freedom from both interferences and background would allow reliable tropospheric OH measurement to be obtained under virtually any ambient condition of current interest, including interstitial and sampling.

Bradshaw, John↗

H + O3 Fourier-transform infrared emission and laser absorption studies of OH(X2Pi) radical - An experimental dipole moment function and state-to-state Einstein A coefficients

FTIR emission/absorption spectroscopy is used to measure the relative intensities of 88 pairs of rovibrational transitions of OH(X2Pi) distributed over 16 vibrational bands. The experimental technique used to obtain the Einstein A ratios is discussed. The dipole moment function which follows from the intensity ratios along with Einstein A coefficients calculated from mu(r) is presented.

Nelson, David D., Jr.↗

Interface conditions for domain decomposition with radical grid refinement

Interface conditions for coupling the domains in a physically motivated domain decomposition method are discussed. The domain decomposition is based on an asymptotic-induced method for the numerical solution of hyperbolic conservation laws with small viscosity. The method consists of multiple stages. The first stage is to obtain a first approximation using a first-order method, such as the Godunov scheme. Subsequent stages of the method involve solving internal-layer problem via a domain decomposition. The method is derived and justified via singular perturbation techniques.

Scroggs, Jeffrey S.↗

Global average concentration and trend for hydroxyl radicals deduced from ALE/GAGE trichloroethane (methyl chloroform) data for 1978-1990

An optimal estimation inversion scheme is utilized with atmospheric data and emission estimates to determined the globally averaged CH3CCl3 tropospheric lifetime and OH concentration. The data are taken from atmospheric measurements from surface stations of 1,1,1-trichloroethane and show an annual increase of 4.4 +/- 0.2 percent. Industrial emission estimates and a small oceanic loss rate are included, and the OH concentration for the same period (1978-1990) are incorporated at 1.0 +/- 0.8 percent/yr. The positive OH trend is consistent with theories regarding OH and ozone trends with respect to land use and global warming. Attention is given to the effects of the ENSO on the CH3CCl3 data and the assumption of continuing current industrial anthropogenic emissions. A novel tropical atmospheric tracer-transport mechanism is noted with respect to the CH3CCl3 data.

Prinn, R.↗

Saturated fluorescence measurements of the hydroxyl radical in laminar high-pressure C2H6/O2/N2 flames

Saturation of a transition of the OH molecule in high-pressure flames is demonstrated by obtaining saturation curves in C2H6/O2/N2 laminar flames at 1, 6.1, 9.2, and 12.3 atm. Quantitative fluorescence measurements of OH number density at pressures to 12.3 atm are presented. To assess the efficacy of the balanced cross-rate model for high-pressure flames, laser-saturated fluorescence measurements, which were calibrated in an atmospheric-pressure flame, are compared with absorption measurements at 3.1 and 6.1 atm. At 3.1 atm the absorption and fluorescence measurements compare well. At 6.1 atm, however, the concentrations given by lasre-saturated fluorescence are about 25 percent lower than the absorption values, indicating some depletion of the laser-coupled levels beyond that at atmospheric pressure. By using a reasonable estimate for the finite sensitivity to quenching, it is anticipated that fluorescence measurements that are calibrated at 1 atm can be applied to flames at about 10 atm with absolute errors within +/- 50 percent.

Carter, Campbell D.↗

Free radical and overtone spectroscopy

In the fall of 1987 during a photoacoustic study of hydrogen peroxide's fourth vibrational overtone band, the remarkably clear and well resolved spectrum was observed. Its periodicity and K subband structure suggested that the spectrum was not of hydrogen peroxide but of a smaller near-prolate symmetric top molecule. Furthermore, the time dependent behavior of the signal indicated that chemical changes were taking place within the photoacoustic apparatus.

Reilly, James P.↗