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At least 127 records · Page 7

A kinetics investigation of several reactions involving chlorine containing compounds

The technique of flash photolysis-resonance fluorescence was utilized to study nine reactions of stratospheric importance. The tropospheric degradation reactions of seven halogenated hydrocarbons were studied to assess their possible influx into the stratosphere. There are reactions of either Cl, OH, or O(3P) species with hydrogenated species, O3 or chlorinated compounds. Apart from the kinetic measurements, the quantum yield for the production of O(1D) from O3 in the crucial wavelength region of 293 to 316.5 nm was studied by utilizing a narrow wavelength laser as the photolysis source. The product formation was monitored by measuring the fluorescence of NO2 formed through O(1D) reaction with N2O followed by NO reaction with O3 to give NO2.

Davis, D. D.↗

Temperature dependence of the rate constants for reactions of O/1D/ atoms with a number of halocarbons

Results are reported for an experimental study of the reactions of O(1D) with CCl4, CFCl3, CF2Cl2, CHFCl2, CHF2Cl, and CF2ClCFCl2 over the temperature range from 173 to 343 K, based on the time-resolved emission of O(1D) at 630 nm. The experiments involved photolysis of O3 by Nd-YAG laser pulses and measurements of 630-nm emission intensity in mixtures with He and the various halocarbons. Pseudo-first-order rate constants are derived from plots of the logarithms of the 630-nm emission intensities as a function of time for particular He/O3/halocarbon mixtures, and second-order rate constants are then obtained from plots of these pseudo-first-order rate constants as a function of halocarbon concentration at constant He and O3 concentrations. No temperature dependence of the second-order rate constants is observed over the range studied, within the precision of the measurements. It is found that the rate constants decrease as H is substituted for Cl in a halocarbon molecule and as F is substituted for H or Cl.

Davidson, J. A.↗

Production of OH from photolysis of HOCl at 307-309 nm

Laser-induced fluorescence has been used to measure the amount of OH produced in the laser photolysis of HOCl at 310 nm. The HOCl was generated by the Cl2O + H2O and by the HCl + Cl2O reactions. The laser technique samples OH on a microsecond time scale so that secondary radical reactions cannot contribute significantly to the observed signals. The fluorescence signals were calibrated with O3-H2O mixtures, the reactions O3 + h(nu) yields O(1D) + O2 and O(1D) + H2O yields 2OH yielding known amounts of OH. The value for the absorption cross section of HOCl at 310 nm has been determined to be 6 x 10 to the -20th sq cm, assuming K(eq) = 0.082 for the Cl2O + H2O yields 2HOCl system and assuming unit quantum yield for the production of OH. The present investigation further supports earlier experimental work concluding that HOCl will photodissociate rapidly and will not be an important holding tank for chlorine in the stratosphere. These results are in disagreement with theoretical calculations of the UV absorption spectrum of HOCl in the 300-350-nm wavelength region.

Molina, M. J.↗

Ozone photolysis - Determination of the O/3P/ quantum yield at 266 nm

Direct production of O(3P) from the photodissociation of O3 at 266 nm has been observed by time-resolved resonance fluorescence following laser flash photolysis. The quantum yield for O(3P) production was determined to be 0.12 + or - 0.02 at this wavelength. This result confirms the qualitative observations of two previous photofragment studies and establishes an absolute value of the quantum yield for O(1D) production of 0.88. This value has been used as a basis for normalizing relative quantum yields in the fall-off region, and interpreting O(1D) kinetics studies.

Brock, J. C.↗

Stratospheric eddy diffusion coefficients from tracer data

Global distributions of nitrous oxide, methane, ozone, and carbon 14 are used to estimate four sets of stratospheric eddy diffusion coefficients. A photochemical equilibrium model calculates O(3P), O(1D), H, HO2, OH, H2O2, NO, and NO2 densities, as a function of altitude, latitude, and time. The calculated O(1D), OH, and observed Cl densities are used to obtain the eddy profiles associated with the methane and nitrous oxide distributions, for altitudes between 10 and 40 km. Application of a constant flux condition to the seasonally averaged ozone data yields eddy values below 20 km. Time-dependent carbon 14 calculations produce eddy coefficients between 13 and 27 km. A composite profile is obtained by comparing the four sets of coefficients. Further, carbon 14 computations are used to test these profiles as well as those recommended in reports issued by the National Academy of Sciences in 1976 and 1979. The composite eddy profile produces the best agreement.

Massie, S. T.↗

Temperature dependence of ozone absorption cross section, 280 to 330 nm

A description is presented of the results of an analysis of the presently available data on the variation of the ozone absorption cross section and the O(1D) yield with temperature. The data used in the analysis of the total ozone cross section were obtained by Inn and Tanaka (1953), Vigroux (1953), and Simons et al. (1973). The O(1D) yield data examined include those of Moortgat et al. (1977), Arnold et al. (1977), and Brock and Watson (1980). For the purposes of the analysis the yield measurements were converted to partial cross sections by multiplying the published yield by the published total cross section.

Hudson, R. D.↗

Concerning sources of O/1D/ in Aurora - Electron impact and dissociative recombination

The present investigation is concerned with two questions. One is related to the possibility that the O(1D) level is produced by an as yet unidentified process in aurora. The second question is concerned with the need for an additional source and the altitude over which it is required. The data base of the AE satellite (AE-D in particular) was examined for this study. It is found that dissociative recombination and electron impact are inadequate sources of O(1D) in aurora. Nearly 90% of the source function is unidentified below 200 km and about 55% is missing above 250 km. The possibility that thermal electron impact could provide the missing source above 250 km was examined. Calculations showed that the missing source above 250 km could be explained by thermal electron impact if the electron temperatures were approximately 2900 K.

Sharp, W. E.↗

O(1S) from dissociative recombination of O2(+) - Nonthermal line profile measurements from Dynamics Explorer

The measurements reported were made of the O(1S) emission line profile at 5577 A at high spectral resolution with the Fabry-Perot interferometer on the Dynamics Explorer spacecraft. It is found that the line profile has marked nonthermal characteristics in the nightglow. A simple collisional relaxation model is used to analyze the nighttime emission line profiles, measured in the equatorial region. The branching ratio is inferred for the dissociative recombination of O2(+) leading to O(1S). The result reveals that the O(1S) + O(1D) channel is favored over the O(1S). The result reveals that the O(1S) + O(1D) channel is favored over the O(1S) + O(3P) channel by a factor of 4; this does not agree with the ratio reported by Hernandez (1971). It is noted, however, that the result is consistent with the active channel for O(1S) production being via the 1Sigma u + repulsive state of O2, as suggested by the theoretical calculations of Guberman (1983). In addition, a value is obtained for the excitation exchange cross section for O(1S).

Killeen, T. L.↗

Luminosity and spatial distribution of the forbidden O I 6300-A emission in comets

The Tuttle, Stephan-Oterna, and Brooks 2 comets have been subjected to CCD observations of the 6300 and 6364 A forbidden oxygen lines, in order to determine the spatial profiles and absolute luminosities of the cometary forbidden O I lines. Analysis indicates the source of the observed O I photons to be direct photodissociation of water vapor. O 1D production by dissociation of OH becomes dominant at larger distances from the nucleus, and the water vapor production rates derived from O I emissions are found to be in good agreement with those determined from forbidden line OH by the IUE spacecraft, as well as ground-based photometry. It is demonstrated that analysis of cometary O 1D emission allows the determination of the spatial distribution of the parent molecule water vapor.

Fink, U.↗

Products and yields from O3 photodissociation at 1576 A

An analysis has been made of the primary atomic and molecular products arising from O3 photodissociation at 1576 A. The yield of oxygen atoms is 1.90 + or - 0.30, of which 71 percent are O(3P) and 29 percent are O(1D). Since a primary yield greater than unity can only be a consequence of three-fragment dissociation, these results suggest that fragmentation into three O(3P) atoms, and production of O(1D) plus a singlet oxygen molecule, have comparable yields. Observation of prompt emission in the 7300-8100 A spectral region indicates that the singlet O2 is O2(b 1Sigma + g). Vibrational levels in the range v = 0-6 have been detected, the distribution corresponding to a vibrational temperature of 1000 K.

Taherian, M. R.↗

How close are ground-based Fabry-Perot thermospheric wind and temperature measurements to exospheric values? A simulation study

A computer simulation model of the measurement process for a ground-based Fabry-Perot interferometer (FPI) has been developed and used to study how variations of wind and temperature along the instrument line-of-sight affect the Doppler shift and width of the observed nightglow O(1D) emission line at high spectral resolution. Ground-based-derived temperatures in the nighttime sector of the winter hemisphere are found to give values that are representative of the peak O(1D) emission altitude. However, when the vertical temperature gradients are large, the ground-based FPI temperature measurement may differ by as much as about 12 percent from the temperature at the peak emission height. Simulations of the FPI measurement of nighttime thermospheric temperatures show that ground-based-derived temperatures may be lower by about 10 percent than the corresponding exospheric temperatures in the winter hemisphere and by about 15 percent in the summer hemisphere.

Mccormac, F. G.↗

Gaseous cometary coronal

Ground-based observations of coma emission line profiles permit direct insight into the composition and kinetic state of a cometary atmosphere and in turn provide much needed constraints in reconstructing a comet's history; the profiles themselves yield information on the mechanisms generating the observed species, while their intensities correspond to overall production rates by the nucleus. Intensities and line profiles at wavelength 6562.1A (H-alpha) and 6300.3A (O(1D) deday) were obtained for Comet Halley in the period March - April 1986 and for Comet Wilson in the period March 1987 using the Fabry-Perot optical facility at Arecibo; the Comet Halley observations have been undergoing careful analysis as the main effort of this project. Attention was centered on O(1D) 6300A observations obtained over four consecutive nights in April 1986. Surprisingly, the sorts of profiles to be expected in coma observations have not been theoretically developed in the past, necessitating a reappraisal of this question. It turns out that coma profiles vary noticeably according to excitation mechanism, and the proper interpretation of a profile requires the use of the appropriate model type. A paper cataloging the basic types and their interpretation will be submitted for publication in a few months. The intensities of the 6300A emission can be used independently to estimate the production rate of H2O by the comet nucleus; indeed, this may be the most reliable way of determining this basic quantity using ground-based facilities. The H2O production rates implied by our observations throughout the period March-April 1986 have been derived and are to be presented at the upcoming COSPAR special session Aeronomy of Comets and Outer Planets.

Atreya, Sushil K.↗

Imaging and spectroscopy of Comet P/Halley

The goals of this investigation are the analysis of a large set of high-resolution echelle/reticon spectra, and the reduction and analysis of a set of narrow-band-filtered charge coupled device (CCD) images of Comet Halley taken during the preperihelion period at Oak Ridge Observatory by Dr. R. E. McCrosky. The scientific objectives associated with these goals are the determination of the spatial distributions of several important radicals, atoms and ions in the coma. These include C2, CN, C3, H2O(+) and CO(+) from the image data. The analysis of the neutral species distribution with Monte Carlo models will aid in the understanding of their production and decay mechanisms as well as serve as an important indicator of the physical conditions in the inner coma. The spatial distributions of the ions will serve as a guide to constrain the complex model necessary for understanding the interaction of the solar wind and the cometary ions. Work during this past year has been devoted largely to the reduction of the standard star photometry for the CCD image data set, as well as the re-flat-fielding of a number of the comet images. We are pleased to report that despite a number of setbacks and the small effort devoted to this work (2 1/2 months for the PI and a generous share of completely unsupported time by Dr. McCrosky) that this portion of the work has been successfully completed. The goals for the upcoming final year of this project (under a new project number) are to complete the calibration of the CCD image data for inclusion in the IHW archive, to analyze a select portion of the neutral radical images with our Monte Carlo models, and to present the results of the 6300/region spectra as a guide to low-resolution spectral observers in order to yield the unambiguous separation of the contributions of cometary O(1D), airglow O(1D), and the numerous NH2 lines in that region of the spectrum.

Combi, Michael R.↗

Modeling and simulation of InP homojunction solar cells

Modeling and simulation of single-crystal InP homojunction solar cells has been performed using the PC-1D code. Cell design and performance have been optimized using the best available estimates of the various materials parameters. A comparison has been made of the predictions of the PC-1D model to those of other models. The optimum performance is predicted to give an efficiency approaching 21 percent at AM0. It is shown that in order to describe the performance of actual cells it is necessary to use larger values of the intrinsic carrier concentration and the surface recombination velocity (SRV) than have been reported in the literature. However, even with a near-maximum value of SRV (e.g., 10 to the 7th cm/s) it is necessary to reduce the minority carrier diffusion length in the emitter to only 0.01 micron in order to account for the relatively low quantum efficiency in the blue part of the spectrum. This indicates that improvement in the emitter bulk properties could be much more important than the SRV. Other loss mechanisms are also discussed; in particular, it is shown that recombination in the base, for good quality material, is relatively insignificant.

Yahia, A. H.↗

The red and green lines of atomic oxygen in the nightglow of Venus

O(1D) and O(1S), the excited states that give rise to the atomic oxygen red and green lines, are produced in the Venus nightglow in dissociative recombination of O2(+). The emissions should also be excited by precipitation of soft electrons, the suggested source of the 'auroral' emission features of atomic oxygen at 1304 and 1356 A, which have been reported from observations of the Pioneer Venus Orbiter Ultraviolet Spectrometer. No emisison at 6300 or 5577 A was detected, however, by the visible spectrophotometers on the Soviet spacecraft Veneras 9 and 10; upper limits have been placed on the intensities of these features. The constraints placed on models for the auroral production mechanism by the Venera upper limits by modeling the intensities of the red and green lines in the nightglow are evaluated, combining a model for the vibrational distribution of O2(+) on the nightside of Venus with rate coefficients recently computed by Guberman for production of O(1S) and O(1D) in dissociative recombination of O2(+) from different vibrational levels. The integrated overhead intensities are 1 - 2 R for the green line and about 46 R for the red line.

Fox, J. L.↗

The effect of varying Mach number on crossing, glancing shocks/turbulent boundary-layer interactions

Two crossing side-wall shocks interacting with a supersonic tunnel wall boundary layer have been investigated over a Mach number range of 2.5 to 4.0. The investigation included a range of equal shock strengths produced by shock generators at angles from 4.0 to 12.0 degrees. Results of flow visualization show that the interaction is unseparated at the low shock generator angles. With increasing shock strength, the flow begins to form a separated region that grows in size and moves forward and eventually the model unstarts. The wall static pressures show a symmetrical compression that merges on the centerline upstream of the inviscid shock locations and becomes more 1D downstream. The region of the 1D pressure gradient moves upstream with increasing shock strengths until it coincides with the leading edge of the shock generators at the limit before model unstart. At the limiting conditions the wall pressure gradients are primarily in the axial direction throughout.

Hingst, W. R.↗

Rapid tuning CW laser technique for measurements of gas velocity, temperature, pressure, density, and mass flux using NO

An intracavity-doubled rapid-tuning CW ring dye laser was used to acquire fully resolved absorption profiles of NO line pairs in the A-X band at 225 nm at a rate of 4 kHz. These profiles were utilized for simultaneous measurements of flow parameters in the high-speed 1D flows generated in a shock tube. Velocity was determined from the Doppler shift, measured using a pair of profiles simultaneously acquired at different angles with respect to the flow direction. Temperature was determined from the intensity ratio of the adjacent lines. Pressure and density were found both from the collisional broadening and the fractional absorption. From this information the mass flux was determined. The results compare well to 1D shock calculations.

Chang, Albert Y.↗

On the efficiency of solar heating in the middle atmosphere

The efficiency at which solar ultraviolet radiation absorbed in the Hartley band of ozone is directly converted to heat in the terrestrial mesosphere and lower thermosphere (50-110 km) is calculated. The ozone molecule undergoes photolysis to yield the excited species O(1D) and O2(1Delta) with a quantum yield of about 0.9. Spontaneous emission from O2(1Delta) and from O2(1Sigma) (excited by energy transfer from O/1D/) significantly decreases the amount of energy available for heat. Similarly, the efficiency at which solar ultraviolet radiation absorbed by O2 in the Schumann-Runge continuum is directly converted to heat in the lower thermosphere (95-110 km) is calculated. The O2 undergoes photolysis and the excited product O(1D) is generated. Spontaneous emission from O2(1Sigma) (excited by energy transfer from O/1D/) reduces the amount of energy available for heat in the lower thermosphere. The consideration of these energy transfer and loss processes results in significantly reduced heating rates as compared to those conventionally calculated in models of the middle atmosphere.

Mlynczak, Martin G.↗