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At least 235 records · Page 13

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.↗

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.↗

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.↗

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.↗

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.↗

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.↗

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↗

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.↗

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.↗

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.↗

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↗

Electron-impact ionization and electron attachment cross sections of radicals important in transient gaseous discharges

Electron-impact ionization and electron attachment cross sections of radicals and excited molecules were measured using an apparatus that consists of an electron beam, a molecular beam and a laser beam. The information obtained is needed for the pulse power applications in the areas of high power gaseous discharge switches, high energy lasers, particle beam experiments, and electromagnetic pulse systems. The basic data needed for the development of optically-controlled discharge switches were also investigated. Transient current pulses induced by laser irradiation of discharge media were observed and applied for the study of electron-molecule reaction kinetics in gaseous discharges.

Lee, Long C.↗

Kinetics and thermochemistry of polyatomic free radicals: New results and new understandings

An experimental facility for the study of the chemical kinetics of polyatomic free radicals is described which consists of a heatable tubular reactor coupled to a photoionization mass spectrometer. Its use in different kinds of chemical kinetic studies is also discussed. Examples presented include studies of the C2H3 + O2, C2H3 + HC1, CH3 + O, and CH3 + CH3 reactions. The heat of formation of C2H3 was obtained from the results of the study of the C2H3 + HC1 reaction.

Gutman, David↗

A laboratory investigation of the production and properties of molecular and radical species pertinent to planetary atmospheres

Vinylidene (H2C=C) is shown to be the largest photodecomposition channel in the direct photolysis of both C2H2 and C2H4. The chemistry of H2C=C as it relates to planetary atmospheres is discussed. The vinyl radical (C2H3), important in the acetylene chemistry cycle, has been directly observed spectroscopically and the kinetics of several key reactions of this species measured.

Fahr, Askar↗

The rotational spectrum of the CH radical in its a 4Sigma(-) state, studied by far-infrared laser magnetic resonance

The CH radical has been detected in its a 4Sigma(-) state by the technique of laser magnetic resonance at far-infrared wavelengths. Spectra relating to different spin components of the first three rotational transitions have been recorded. The molecule was generated either by the reaction of F atoms with CH4, with a trace of added oxygen or by the reaction of O atoms with C2H2. The observed resonances have been analyzed and fitted to determine the parameters of an effective Hamiltonian for a molecule in a 4Sigma state. The principal quantities determined are the rotational constant B0 = 451 138.434(94) MHz and the spin-spin parameter lambda(0) = 2785.83(18) MHz. Proton hyperfine parameters have also been determined.

Nelis, Thomas↗

Ground and lower excited states of methyl peroxy, CH3O2, radical - A computational investigation

The ground and lower excited states of methyl peroxy, CH3O2, radical have been investigated at the selected pseudofirst-order configuration interaction level by use of a double-zeta basis set. Selected singles and doubles calculations using a polarized double-zeta basis have been carried out on the two lowest states in the A-double prime symmetry. Dissociation energies with respect to CH3O2 yields CH3 + O2 and CH3O + O are computed to be 2.01 and 3.37 eV, respectively. Curve crossings between various states and photodissociation products are discussed and the dipole moment along various slices through the potential energy surface is evaluated.

Jafri, Jawed A.↗

Third-generation FAGE instrument for tropospheric hydroxyl radical measurement

A single-stage, frequency-doubled, copper vapor laser-pumped dye laser has been constructed to be used in the measurement of atmospheric hydroxyl radical concentrations. A new photon counting instrument is used for HO fluorescence detection. Theoretical and experimental studies of instrument performance show better sensitivities and reduced photolytic interferences than have been possible with previous systems based upon Nd:YAG pumping.

Chan, C. Y.↗

Carbon kinetic isotope effect in the oxidation of methane by the hydroxyl radical

The reaction of the hydroxyl radical (HO) with the stable carbon isotopes of methane has been studied as a function of temperature from 273 to 353 K. The measued ratio of the rate coefficients for reaction with (C-12)H4 relative to (C-13)H4 (k12/k13) was 1.0054 (+ or - 0.0009 at the 95 percent confidence interval), independent of temperature within the precision of the measurement, over the range studied. The precision of the present value is much improved over that of previous studies, and this result provides important constraints on the current understanding of the cycling of methane through the atmosphere through the use of carbon isotope measurements.

Cantrell, Christopher A.↗