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At least 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
NASA NTRS1977

A survey of interstellar molecular hydrogen. I

Data from the Copernicus satellite's ultraviolet telescope were used to survey column densities of atomic and molecular hydrogen from a large sample of early-type stars; these data have bearing on an eventual understanding of diffuse and dense interstellar clouds. Column densities are derived by fitting damping profiles to the observed spectra, most of which exhibit strong damping lines in the lower rotational levels surveyed. Plots of dust column density, fractional abundance of molecular hydrogen, and the logarithm of fractional abundance versus total gas column density are given for many of the stars; stars with abnormally large or small hydrogen column densities, as well as some distant stars at high galactic latitudes, are considered. Equilibrium and nonequilibrium theories accounting for the abundance of interstellar hydrogen are compared, and support is found in the data for an account which balances hydrogen formation on interstellar grains with destruction through photodissociation. Overall averages for atomic and molecular hydrogen levels in the galactic plane are also calculated.

Savage, B. D.↗
NASA NTRS1977

Flash photolysis resonance fluorescence investigation of the reaction of Cl/2P/ atoms with ClONO2

Rate constants for the removal of Cl(2P) atoms by homogeneous gas phase reaction with ClONO2 were measured using the flash photolysis resonance fluorescence technique at 224, 250, and 273 K. The values obtained have been used to derive the above Arrhenius equation. The uncertainties expressed are 95% confidence limits obtained using the statistical standard deviation of the individual rate constants plus a 15% additional estimated uncertainty attributed to difficulties in chlorine nitrate concentration measurements. The results indicate that destruction of chlorine nitrate by reaction with chlorine atoms is perhaps the least important of the atmospheric reactive channels, and is at least three orders of magnitude slower than calculated photodissociation rates at all stratospheric altitudes.

Kurylo, M. J.↗
NASA NTRS1977

Laser induced photoluminiscence studies of primary photochemical production processes of cometary radicals

A tunable vacuum ultraviolet flash lamp was constructed. This unique flash lamp was coupled with a tunable dye laser detector and permits the experimenter to measure the production rates of ground state radicals as a function of wavelength. A new technique for producing fluorescent radicals was discovered. This technique called multiphoton ultraviolet photodissociation is currently being applied to several problems of both cometary and stratospheric interest. It was demonstrated that NO2 will dissociate to produce an excited fragment and the radiation can possibly be used for remote detection of this species.

Jackson, W. M.↗
NASA NTRS1976

Broadband photoexcitation of lasers

Existing techniques are reviewed and novel approaches for broadband photoexcitation of lasers are discussed. This subject is of interest because of the emergence of future intense near equilibrium and blackbody sources, such as the gas core reactor, and electric discharge plasma devices, which are the key to the development of intense broadband radiation sources. The possible use of radiation from solar concentrators in space also fits into this general area. The varied use of photoexcitation of lasers are discussed ranging over direct optical pumping, photodissociation, and photoreionization. In addition, the new uses of laser transitions and chemical reactions is shown. This is accomplished through multiline operation of high pressure tunable lasers which can use the broadband radiation for multiphoton excitation.

Hess, R. V.↗
NASA NTRS1977

The effects of thermospheric winds and chemistry in the diurnal variations of thermospheric species

The reported investigation considers on the basis of a theoretical model, the diurnal variations of the thermospheric composition (H, He, O, O2, and Ar) in terms of thermal expansion with diffusive equilibrium and transport effects associated with thermospheric winds, chemistry, and exospheric flow. The theoretical results are compared with satellite composition data which indicate that the fundamental diurnal tide can be reasonably well understood. It is found that winds are only important for molecular oxygen below 180 km, while thermal expansion due to the larger mass is relatively more important for O2 than for O. Distinct from O, photodissociation and in particular photoionization of O2 are very significant for molecular oxygen.

Mayr, H. G.↗
NASA NTRS1977

Ultraviolet absorption spectrum of hydrogen peroxide vapor

The ultraviolet absorption cross sections of hydrogen peroxide vapor have been determined over the wavelength range 210 to 350 nm at 296 K. At the longer wavelengths, the gas phase absorptivities are significantly larger than the corresponding values in condensed phase. The atmospheric H2O2 photodissociation rate for overhead sun at the earth's surface is estimated to be about 1.3 x 10 to the -5th/sec.

Molina, L. T.↗
NASA NTRS1978

Vibrational excitation of H2 in intense ultraviolet fluxes

The vibrational excitation of H2 in intense ultraviolet radiation fields is studied. The radiative cascade through bound levels of the ground electronic state, following absorption of Lyman- and Werner-band photons, is modified to include effects of 'multiple pumping' and direct photodissociation from the high vibrational levels. Although the column densities in the excited vibrational levels produced by UV pumping appear too low to explain the recently observed Orion quadrupole emission lines, it is suggested that the far-red lines in the (3-0) and (4-0) bands, produced by UV pumping from O stars near dense molecular clouds, may be detectable.

Shull, J. M.↗
NASA NTRS1978

Ozone profiles and chemical loss rates in the tropical stratosphere deduced from backscatter ultraviolet measurements

Analysis of data obtained by the backscatter ultraviolet (BUV) experiment on the Atmosphere Explorer E satellite has provided equatorial ozone mixing ratio profiles for equinox and solstice conditions. The combination of these results with a pure oxygen chemical model yields the rate of odd oxygen loss due to the sum of the odd hydrogen, nitrogen, and chlorine cycles. Use of recent mid-latitude stratospheric measurements of HO(x), NO(x), and ClO(x) with the BUV data provides an independent calculation of the catalytic loss. Below 45 km the agreement between the two sets of loss rates is satisfactory. At higher altitudes the odd hydrogen cycle provides far more O(x) loss than can be tolerated by the BUV measurements if the photodissociation of O2 is the only source and has the currently accepted magnitude. The results suggest either a tropical HO(x) concentration smaller than is now believed or the presence of a very large source of odd oxygen in the upper stratosphere and lower mesosphere.

Frederick, J. E.↗
NASA NTRS1978

Ultraviolet absorption cross sections of hydrogen peroxide

Absorption cross-sections of hydrogen peroxide vapor and of neutral aqueous solutions of hydrogen peroxide were measured in the wavelength range from 195 to 350 nm at 296 K. The spectrophotometric procedure is described, and the reported cross-sections are compared with values obtained by other researchers. Photodissociation coefficients of atmospheric H2O2 were calculated for direct absorption of unscattered solar radiation, and the vertical distributions of these coefficients are shown for various solar zenith angles.

Lin, C. L.↗
NASA NTRS1977

Photodecomposition of chloromethanes adsorbed on silica surfaces

Irradiation of CCl4, CFCl3, and CF2Cl2 in the presence of C2H6 in vessels containing silica sand or fused quartz tubing results in the formation of chlorine-containing products. The formation of these compounds occurs at wavelengths extending up to approximately 400 nm, that is, at wavelengths well beyond the absorption threshold of the chloromethanes in the gas phase. It is suggested that CCl4 adsorbed on silica surfaces photodissociates to yield CCl3 and CCl2 species. The poor material balance obtained in these experiments indicates that several of the chlorine-containing fragments are strongly adsorbed on the surface. At a CCl4 pressure of 13 Pa (0.1 torr), photolysis with 366 nm light in the presence of sand results in the decomposition of one molecule for every 10,000 photons striking the surface. Under otherwise identical conditions, the photon-induced breadkdown of CFCl3 and CF2Cl2 is respectively only 10% or 3% as efficient.

Ausloos, P.↗
NASA NTRS1977

A new concept in laser-assisted chemistry - The electronic-field representation

Electronic-field representation is proposed as a technique for laser-assisted chemistry. Specifically, it is shown that several field-assisted chemical processes can be described in terms of mixed matter-field quantum states and their associated energies. The technique may be used to analyze the effects exerted by an intense laser on both bound and unbound molecular systems, and to investigate other field-induced effects including multiphoton processes, emission, and photodissociation.

George, T. F.↗
NASA NTRS1978

A note on the diurnal averaging of aeronomical models

An approximate technique for diurnally time-averaging atmospheric photochemical-dynamical models which eliminates the need for a detailed numerical resolution of sunrise and sunset transitions is developed. The scheme is equivalent to scaling certain chemical rate constants and photodissociation coefficients by appropriate aeronomical factors. To calculate the scaling factors, diurnal variations are parameterized with a step-function behavior, assuming that each species has a constant day-time and night-time concentration whose ratio can be determined by analyzing the chemical interactions occurring after sunset. The solution accounts for the effects of night-time reactions on the 24 h average values of species abundances, and on the average daily rates of the catalytic processes consuming ozone in the stratosphere. The accuracy of the technique is demonstrated by comparing its predictions to those of a full diurnal simulation; typically, the precision is better than 10%. By contrast, it is shown that the use of some other well-known computational schemes can result in significantly larger predictive errors.

Turco, R. P.↗
NASA NTRS1978

Semiclassical theory of unimolecular dissociation induced by a laser field

A semiclassical nonperturbative theory of direct photodissociation in a laser field is developed in which photon absorption and dissociation are treated in a unified fashion. This is achieved by visualizing nuclear dynamics as a representative particle moving on electronic-field surfaces. Methods are described for calculating dissociation rates and probabilities by Monte Carlo selection of initial conditions and integration of classical trajectories on these surfaces. This unified theory reduces to the golden rule expression in the weak-field and short-time limits, and predicts nonlinear behavior, i.e., breakdown of the golden rule expression in intense fields. Field strengths above which lowest-order perturbation theory fails to work have been estimated for some systems. Useful physical insights provided by the electronic-field representation have been illustrated. Intense field effects are discussed which are amenable to experimental observation. The semiclassical methods used here are also applicable to multiple-surface dynamics in fieldfree unimolecular and bimolecular reactions.

Yuan, J.-M.↗
NASA NTRS1978

The O I /6300 A/ airglow

The production and destruction of O(D-1) atoms in the thermosphere are studied on the basis of observations conducted by the Atmosphere Explorer-C spacecraft. In particular, measurements of the O I transition at 6300 A provide a means of calculating the strength of the O2(+) dissociative recombination source of O(D-1), which amounts to 1.33. A value of 3 times 10 to the minus 11th power cu cm/sec is established for the quenching rate of O(D-1) by molecular nitrogen, while the photodissociation rate for O2 is set at three millionths per sec. These determinations are in agreement with the conventional theory of the day 6300-A airglow.

Hays, P. B.↗
NASA NTRS1978

On the detection of newly created CN radicals in comets

A description is presented of laboratory measurements concerning the amount and the distribution of energy released into newly formed radicals by the photodissociation process. The experimental method used involved flash photolysis of the parent compound followed by laser induced fluorescence detection of the CN fragment. This method allowed the detection of individual rotational lines and, thereby, a monitoring of the relative populations of the vibrational-rotational levels of the CN ground state. The results obtained in the investigation suggest the possibility of observing emission lines in cometary spectra from newly formed CN radicals. Calculations show that it is feasible with present observational techniques to detect photochemically excited lines in the 0-0 band of the violet system.

Donn, B.↗
NASA NTRS1978

Measurement of solar radiation at ground level in the region 1950-2150 A using ammonia actinometry

The use of ammonia as an actinometer for measurement of the solar flux in the region 1950-2150 A is presented. The solar flux was found to be 270 million photons/sq cm per sec at ground level in this wavelength interval in an area with minimum overhead ozone concentration. The advantages of this method over previously used methods are discussed, and the results are related to the present estimates of the tropospheric photodissociation rates for the freons CFCl3 and CF2Cl2 by radiation in this wavelength region.

Knoot, P.↗
NASA NTRS1978

An analysis of the coma of comet Bennett 1970 II

Brightness profiles for emission features of H2O(+) in comet Bennett 1970 II are analyzed, taking into account the role of chemical reactions in the coma. By comparing the rates of transport processes derived from the brightness profile with known chemical rate constants, upper limits on the abundances and production rates of H2O, CH4, NH3, and other possible coma constituents are found. The derived upper limit on the H2O production rate inside 10 to the 4th power km is less than the observed OH production rate averaged over the coma of this comet. It is concluded that the brightness profiles of H2O(+) and OH in comet Bennett 1970 II which are presently available are inconsistent with production of OH primarily by photodissociation of H2O molecules sublimating from the nucleus. The existence of an extended source of H2O is not ruled out.

Oppenheimer, M.↗
NASA NTRS1978

The ammonia mixing ratio in Jupiter's stratosphere

The paper describes the theory that underlies the model calculations which show that the far-infrared bands of ammonia are very sensitive to the ammonia distribution above the Jovian atmospheric inversion layer. Observation of the J = 5 and J = 6 ammonia bands at moderate resolution might permit choice between a cold trap model or the irreversible uv photodestruction model for the ammonia distribution. The lack of prominent emission cores in the NH3 rotation-inversion lines only implies that the mixing ratio is low. The ammonia is uniformly mixed if the inversion temperature is low but, at a higher inversion temperature, emission cores will be observed unless the photodissociation is extremely efficient down to at least the inversion layer.

Goorvitch, D.↗