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At least 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
NASA NTRS1985

Free radicals in the stratosphere - A new observational technique

A new approach to in situ observations of trace reactive species in the stratosphere is described. A balloon-borne system, floating 40 kilometers above the earth's surface, successfully lowered and then retracted a cluster of instruments a distance of 12 kilometers on a filament of Kevlar. This instrument cluster is capable of detecting gas-phase free radicals at the part-per-trillion level. The suspended instrument array has excellent stability and has been used to measured atomic oxygen concentrations in the stratosphere.

Anderson, J. G.↗
NASA NTRS1985

Astronomical identification of the C3H radical

The C3H radical has been identified in the millimeter-wave spectra of IRC +10216 and TMC-1. In IRC +10216, four rotational transitions have been observed, three in the lower fine-structure ladder (2Pi1/2) and one in the upper (2Pi3/2), each a resolved or partially resolved lambda-doublet. In TMC-1, both lambda components of the lowest lying 3/2-1/2 transition of the 2Pi1/2 ladder have been observed, each with well-resolved hfs. In IRC +10216, the excitation of C3H is similar to that of SiCC: the rotational temperature Trot within the 2Pi1/2 ladder is low (8.5 K), because of rapid radiative decay, while Trot across the ladders is high (about 52 K), because interconnecting far-IR radiative transitions are only weakly permitted. The column density of C3H in IRC +10216 averaged over the estimated source diameter of 84 arcsec is 2.8 x 10 to the 13th/sq cm, an order of magnitude less than that of C2H and C4H.

Thaddeus, P.↗
NASA NTRS1985

Laboratory detection of the C3H radical

Millimeter-wave lines of the C3H radical, including six of the lines observed in space, were detected in a laboratory glow discharge through a flowing mixture of C2H2, He, and CO. Each of the 10 rotational transitions measured, five between 98 and 185 GHz in the 2Pi1/2 ladder and five between 80 and 194 GHz in the 2Pi3/2 ladder, is split by lambda-type doubling, and all but three possess resolved hyperfine structure. The excellent agreement between the fine-structure, rotation, lambda-doubling, and hyperfine constants derived from the laboratory data and from the astronomical observations conclusively confirms the identifications in IRC +10216 and TMC-1 by Thaddeus and colleagues (1985). An accurate set of spectroscopic constants, which allow calculation of the entire radio spectrum of C3H to a radial velocity of 0.1 km/s, was derived from a simulataneous fit to the laboratory frequencies and to the well-resolved hfs observed in the narrow-line astronomical source TMC-1.

Gottlieb, C. A.↗
NASA NTRS1985

Cometary atmospheres: Modeling the spatial distribution of observed neutral radicals

The analysis of observed brightness profiles for the C2 radical in comets with Haser's model implies that the parent scale length varies as the square of the heliocentric distance. The use of new Haser scale lengths for C2 and CN determined under this project appears to explain the apparent drop in the C2-to-CN ratio with increasing heliocentric distance.

Combi, M. R.↗
NASA NTRS1986

Cometary atmospheres: Modeling the spatial distribution of observed neutral radicals

New data for the spatial distribution of cometary C2 are presented. A recompilation of the Haser scale lengths for C2 and CN resolves the previously held anomalous drop of the C2/CN ratio for heliocentric distances larger than 1 AU. Clues to the source of cometary C2 have been found through fitting the sunward-antisunward brightness profiles with the Monte Carlo particle-trajectory model. A source (parent) lifetime of 3.1 x 10,000 seconds is found, and an ejection speed for C2 radicals upon dissociation of the parent(s) of approx. 0.5 km 1/5 is calculated.

Combi, M. R.↗
NASA NTRS1985

Infrared and far-infrared laser magnetic resonance spectroscopy of the GeH radical - Determination of ground state parameters

The GeH radical has been detected in its ground 2 Pi state in the gas phase reaction of fluorine atoms with GeH4 by laser magnetic resonance techniques. Rotational transitions within both 2 Pi 1/2 and 2 Pi 3/2 manifolds have been observed at far-infrared wavelengths and rotational transitions between the two fine structure components have been detected at infrared wavelengths (10 microns). Signals have been observed for all five naturally occurring isotopes of germanium. Nuclear hyperfine structure for H-1 and Ge-73 has also been observed. The data for the dominant isotope (/Ge-74/H) have been fitted to within experimental error by an effective Hamiltonian to give a set of molecular parameters for the X 2 Pi state which is very nearly complete. In addition, the dipole moment of GeH in its ground state has been estimated from the relative intensities of electric and magnetic dipole transitions in the 10 micron spectrum to be 1.24(+ or - 0.10) D.

Brown, J. M.↗
NASA NTRS1986

The microwave and far-infrared spectra of the O-(18)H radical

Far-infrared laser magnetic resonance (LMR) spectroscopy was used to calculate the frequencies, wavelengths, and line strengths for transitions of O-(18)H molecules at microwave and far-infrared frequencies. In this experiment, a molecular transition frequency is tuned into coincidence with that of a fixed frequency laser by the application of a variable magnetic field. The O-(18)H radicals, detected in natural abundance (0.20 percent), were produced by the reaction of hydrogen atoms with nitrogen dioxide. These data together with microwave frequencies ascertained by Gottlieb, Redford, and Smith (1974) were used to determine the parameters of an effective Hamiltonian. Rotational levels up to J = 5.5 were involved. Results are indicated schematically and the low-lying energy levels of O-(18)H are shown. It is concluded that the frequencies of transitions between levels studied directly in the LMR experiment are reliable.

Comben, E. R.↗
NASA NTRS1986

Cometary atmospheres: Modeling the spatial distribution of observed neutral radicals

Progress during the second year of a program of research on the modeling of the spatial distributions of cometary radicals is discussed herein in several major areas. New scale length laws for cometary C2 and CN were determined which explain that the previously-held apparent drop of the C2/CN ratio for large heliocentric distances does not exist and that there is no systematic variation. Monte Carlo particle trajectory model (MCPTM) analysis of sunward and anti-sunward brightness profiles of cometary C2 was completed. This analysis implies a lifetime of 31,000 seconds for the C2 parent and an ejection speed for C2 of approximately 0.5 km/sec upon dissociation from the parent. A systematic reanalysis of published C3 and OH data was begun. Preliminary results find a heliocentric distance dependence for C3 scale lengths with a much larger variation than for C2 and CN. Scale lengths for OH are generally somewhat larger than currently accepted values. The MCPTM was updated to include the coma temperature. Finally, the collaborative effort with the University of Arizona programs has yielded some preliminary CCD images of Comet P/Halley.

Combi, Michael R.↗
NASA NTRS1987

Laboratory studies of the kinetics of tropospheric and stratospheric atom and radical reactions

Direct measurements of reaction rate constants and branching fractions for elementary reactions necessary in the modeling of the troposphere or stratosphere are provided. Details of reaction mechanisms are elucidated by studying pressure and temperature dependences of reactions, as well as by use of isotopic labels. Measurement techniques are improved for radical species in the laboratory. Progress and results in each area are given.

Golde, Michael F.↗
NASA NTRS1986

Laboratory measurement of the rotational spectrum of the OH radical with tunable far-infrared research

Rotational and fine-structure transitions between the low rotational levels of the OH radical in its X 2Pi state have been observed in absorption in the laboratory. It has thus been possible to measure the frequencies of these transitions directly. The observations were made with tunable far-infrared radiation generated by mixing two chosen CO2 laser frequencies in a metal-insulator-metal diode; the far-infrared difference frequency was radiated from the diode's whisker antenna. The measurements have an accuracy of a few hundred kHz. They both confirm and improve on the best previous estimates, which were obtained by extrapolation of laser magnetic resonance data.

Brown, J. M.↗
NASA NTRS1987

Kinetics of the reactions of SH radicals with NO2 and O2

The SH + NO2 reaction rate constant was measured by monitoring SH concentrations with long-path optical absorption at 324 nm in a laser photolysis system. At 298 K, the rate constant was found to be (4.8 + or - 1.0) x 10 to the -11th cu cm/molecule per sec. An upper limit of 4 x 10 to the -19th cu cm/molecule per sec was inferred for the SH + O2 reaction, indicating that the atmospheric oxidation of the SH radical may occur via reaction with species such as NO2 and O3.

Stachnik, R. A.↗
NASA NTRS1988

Kinetics of CH(X 2Pi) radical reactions with cyclopropane, cyclopentane, and cyclohexane

Rate constants have been obtained for CH(X 2Pi) radical reactions with cyclopropane, cyclopentane, and cyclohexane in order to establish the rate of CH insertion into secondary C-H bonds in alkanes. Data indicate that there is no measurable dependence on photolysis laser energy. The reactions all exhibited rate constants that decrease with increasing temperature. It is suggested that a possible set of pathways for the cycloalkane reactions is a ring-opening process where the excited adduct decomposes to a hydrogen atom and a diene.

Zabarnick, S.↗
NASA NTRS1988

Fourier transform spectroscopy of the nu3 band of the N3 radical

The nu3 transitions of N3 radicals produced by HN3-Cl reactions in a multipass cell (effective path length 100 m) are investigated experimentally using a Fourier-transform spectrometer with maximum resolution 0.004/cm. A total of 176 rotation-vibration lines are listed in a table and used, in combination with published data on 240 optical lines (Douglas and Jones, 1965), to determine the nu3 molecular constants. The lower-than-expected value of the nu3 fundamental frequency (1644.6784/cm) is attributed to the vibronic interaction discussed by Kawaguchi et al. (1981).

Brazier, C. R.↗
NASA NTRS1988

High resolution FTIR spectroscopy of the ClO radical

The chlorine monoxide radical, ClO, plays a significant role in the catalytic destruction of ozone in the Earth's stratosphere. Because of its atmospheric importance, ClO has been the subject of numerous observational attempts. In order to deduce ClO concentrations from stratospheric infrared measurements, the infrared spectroscopy of ClO must be well characterized. Approximately 830 individual lines were measured form ClO imfrared spectra with the ClO concentration between 1 x 10 to the 13th power and 6 x 10 to the 13th power molecules per cu cu. The lines were then averaged and fit to a function of m (where m = O, -J or J+1 for the Q,P and R branches respectively) to obtain the band strength, S sub v and the first Herman-Wallis coefficient, alpha. The total S sub v for the two main isotopmers was 13.11 plus or minus 1 cm(-2) atm(-1) while alpha was 0.00412 plus or minus .00062.

Lang, Valerie↗
NASA NTRS1988

Identification of the interstellar cyanomethyl radical (CH2CN) in the molecular clouds TMC-1 and Sagittarius B2

The astronomical identification of the cyanomethyl radical, CH2CN, in interstellar clouds is reported. The complex fine and hyperfine structures of the lowest rotational transitions at about 20.12 and 40.24 GHz are resolved in TMC-1. The abundance of CH2CN relative to that of H2 in TMC-1 is estimated at 5 X 10 to the -9th. In Sgr B2, the hyperfine structure is blended in the higher frequency transitions at 40, 80, and 100 GHz, although the spin-rotation doubling is clearly evident.

Irvine, W. M.↗
NASA NTRS1988

The determination of absolute ro-vibrational intensities for radical diatomic molecules

Ro-vibrational transition intensities of radical and/or chemically reactive molecular species are difficult to determine. A number of methods which might be used to provide information on matrix elements of the electric dipole moment function and the construction of the dipole moment function from the information these methods provide are discussed. The derived dipole moment function represents an optimum choice and allows a calculation (with estimable errors) of the line intensities for a large number of ro-vibrational transitions.

Chackerian, C., Jr.↗
NASA NTRS1989

Rovibrational intensities for the Delta V = 1 bands of the X 3Sigma(-) NH radical - Experiment and theory

The vibrational transition dipole moment for the highly reactive radical species NH in its ground electronic state is obtained via the Herman-Wallis effect manifest in emission spectra produced in a plasma reactor. The results of these experiments on the five lowest Delta V = 1 bands are in good agreement with high quality ab initio calculations of the electric dipole moment function.

Chackerian, C., Jr.↗
NASA NTRS1989

The mixing ratio of the stratospheric hydroxyl radical from far infrared emission measurements

Far infrared emission spectra of the stratosphere, measured with a 0.0033/cm resolution Fourier transform spectrometer using a limb scanning method, are analyzed in order to retrieve the vertical distribution of the hydroxyl radical (OH). The observations cover a time interval between 1300 and 2300 hours, showing a pronounced time decrease of the OH signals. Vertical profiles are obtained for the afternoon and sunset periods. An upper limit is derived from the small signals present in the night measurements. Three different methods of analysis have been applied to the same data set, and the results provided the basis for a critical discussion of the error sources. The results are compared with theoretical predictions and with the results of other experiments.

Carli, Bruno↗