Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “RADICALS”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 793 records · Page 44

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.↗

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.↗

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.↗

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.↗