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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.

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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
NASA NTRS1986

CF2 and CFCl fluorescence from VUV excitation of C2F3Cl

The photoexcitation process of C2F3Cl molecule was investigated in the 106 to 230 nm region using synchrotron radiation as a light source. Photoabsorption and fluorescence cross sections were measured and used to determine the fluorescence quantum yield. Fluorescence yield starts to appear at 170 nm and increases to about 2% at 155 nm. The fluorescence spectra were dispersed to identify the emitting species. At the excitation wavelength of 155 nm, the emission system is CFCl (Hermitian conjugate of A - Hermitian conjugate of X), and at 123.9 nm, both the CF2 (Hermitian conjugate of A - Hermitian conjugate of X) and CFCl (Hermitian conjugate of A - Hermitian conjugate of X) systems are observed. The dissociation processes that produced these excited species are discussed.

Nee, J. B.↗
NASA NTRS1986

Photochemical production of H2SO4 aerosols on Venus

The quantum yields for producing O2(a (1 delta g)) and O2(b(1 sigma g +)) for the reaction, O + ClO yields Cl + O2, are summarized. Also included are results for other simple reactions capable of producing the singlet oxygen states. An episodic injection of SO2 into the upper atmosphere of Venus is considered as a possible explanation for the airglow values.

Yuk, L. Yung↗
NASA NTRS1986

Laser induced fluorescence and phosphorescence of matrix isolated glyoxal - Evidence for exciplex formation in the A 1Au and a 3Au states

Laser-induced fluorescence and phosphorescence as well as infrared and visible absorption spectra of glyoxal in Ar, N2, and CO matrices are presented and analyzed. Glyoxal in its first excited electronic state is shown to form an exciplex with its nearest neighbors in all three matrices, and transitions normally forbidden dominate the emission spectra. The spectral characteristics of these complexes are similar to those of the Ar-glyoxal complex found in supersonic beam experiments. Due to the matrix cage effect, no vibrational predissociation is observed. The phosphorescence lifetime is determined and an upper limit is given for the fluorescence lifetime. This, in combination with the relative intensities of fluorescence and phosphorescence, can be used to place limits on the quantum yields of the various relaxation processes.

Van Ijzendoorn, L. J.↗
NASA NTRS1986

Fluorescence from VUV excitation of formaldehyde

The 105-180-nm photoabsorption and fluorescence cross sections of H2CO are determined experimentally using a synchrotron-radiation light source and the apparatus described by Lee (1980). The results are presented in tables and graphs and discussed. VUV emission with threshold wavelength 140.3 nm is detected and attributed to the A 1Pi - X 1Sigma(+) system of CO, and UV emission from the HCO (B-X) system is found below a 147.5-nm threshold, the H-HCO dissociation energy having an upper limit of 3.61 + or - 0.03 eV. At 116 nm, the maximum quantum yields of the VUV and UV fluorescences are about 1.6 and 0.23 percent, respectively.

Suto, Masako↗
NASA NTRS1987

The excitation function of OH(A2Sigma/+/ - X2Pi) fluorescence produced through photodissociation of H2O

The absolute cross section for production of OH(A2Sigma/+/ X2Pi) fluorescence through photodissociative excitation of H2O was obtained using the University of Wisconsin synchrotron radiation source. The absolute fluorescence cross section function shows three broad features, roughly centered at 710, 400, and 240 A; the maximum value fluorescence cross section was found to be 3.4 x 10 to the -20th sq cm at 703 A. The broad features in the 700-A and 400-A regions are considered to be due to the second and the third excited states of H2O, respectively; it is argued that the broad feature at 240 A may have an origin similar to that of the 400-A broad feature. From present and previous data on quantum yields, it is estimated that part of the yield may be attributable to the production of neutral ground state OH(X) and H(1 2S) fragments. Such a process could provide a significant source of high kinetic energy OH and H observed in cometary atmospheres.

Wu, C. Y. Robert↗
NASA NTRS1986

Transient gain-versus-absorption laser probing of spin-orbit states, kinetics and dynamics

The spin-orbit populations of excited (2P1/2) and ground (2P3/2) state Br atoms at 2714 nm and I atoms at 1315 nm are examined using a tunable F-center laser and a diode laser. The transient laser gain-versus-absorption measurements are utilized to estimate quantum yields of the spin-orbit states in the photodissociation of Br- and I-containing compounds; the continuum yields for Br2 are investigated in terms of temperature. The collisional release, Doppler velocity effects, and differing reactivity of the spin-orbit excited and ground state atoms are studied. It is noted that the transient gain versus absorption technique is applicable to the analysis of kinetic phenomena due to its high sensitivity and excellent time resolution.

Smedley, John E.↗
NASA NTRS1986

Quantitative photoabsorption and fluorescence study of H2O and D2O at 50-190 nm

The photoabsorption cross sections and the fluorescence quantum yields of H2O and D2O were measured in the 50-190 nm region using synchrotron radiation as a light source. The oscillator strengths for the Rydberg states of H2O and D2O were determined from the absorption cross sections measured. The processes for the production of fluorescence from the excited species H(asterisk) (n greater than 2), D(asterisk) (n greater than 2), OH(asterisk) (A) and OD(asterisk) (A) are discussed. The upper limit for the dissociation energy of D(D-OD) was determined, from the threshold of the OD(A-X) fluorescence, to be 5.14 + or - 0.01 eV. The upper limit for the cross section of visible fluorescence from the excited H2O(+) ions was determined to be 2 x 10 to the -19th sq cm. A comparison between the photoexcitation spectra of H2O and D2O is made.

Lee, L. C.↗
NASA NTRS1987

The production of NH(A 3Pi i) through photodissociative excitation of NH3

The NH(A-X) emission produced by photodissociation of NH3 is examined using a line emission source in the 600-1340 A region. It is observed that the production of the NH(A 3Pi i) photofragment involves a spin-forbidden transition. Fluorescence spectra of NH3 are derived and analyzed. The relationship between fluorescence cross sections and fluorescence count rates and gas pressure is studied. The fluorescence cross sections of NH(A-X) are calculated as 2.1 x 10 to the -22nd, 3.1 x 10 to the -22nd, 3.0 x 10 to the -21st, 1.5 x 10 to the -20th, and 3.4 x 10 to the -20th sq cm for the primary photon wavelength of 1239, 1184, 1065, 1037, and 976 A, respectively; and the corresponding fluorescence quantum yields are 0.00002, 0.00003, 0.0012, 0.0085, and 0.015.

Wu, C. Y. Robert↗
NASA NTRS1987

The photochemistry of some possible cometary CN parent species

Laboratory work on the photochemistry of HC3N, C4N2, and CH3CN in relation to their possible role as CN parent molecules in comets is discussed. Photodissociation of HC3N, photolysis of C4N2, and quantum yields of excited CN(B) and CN(A) radicals from the VUV photolysis of CH3CN are considered.

Halpern, Joshua B.↗
NASA NTRS1987

CF2 and CFCl fluorescence from VUV excitation of C2F3Cl

The photoexcitation process of the C2F3Cl molecule was investigated in the 106-230-nm region using synchrotron radiation as a light source. Photoabsorption and fluorescence cross sections were measured and used to determine the fluorescence quantum yield. Fluorescence yield starts to appear at 170 nm and increases to about 2 percent at 155 nm. The fluorescence spectra were dispersed to identify the emitting species. The (A-X) systems of CFCl (at excitation wavelengths 155 and 123.9 nm) and CF2 (at 123.9 nm) are observed. The dissociation processes that produced these excited species are discussed.

Nee, J. B.↗
NASA NTRS1988

Temperature dependence of the atmospheric photolysis rate coefficient for NO2

Accurate values for the photolysis rate coefficient of NO2 (j1) are required for studies related to the observed imbalance in the photostationary state of O3, NO, and NO2 in the troposphere. Direct measurements of the temperature dependence of j1 at temperatures from -70 to 30 C were made in sunlight for relatively cloudless summer days in Boulder, Colorado. The ratios of j1 (30 C)/j1 (T C) for T = -10 C and -70 C, respectively, were 1.046 + or - 0.040 and 1.070 + or - 0.031. The j1 ratios were independent of solar zenith angle. Theoretical estimates of the temperature-dependent j1 ratios based upon recently reported cross section (sigma) and quantum yield (phi) data are more consistent with these experimental measurements than those based upon the currently accepted sigma and phi data.

Shetter, Richard E.↗
NASA NTRS1988

A new laboratory source of ozone and its potential atmospheric implications

Although 248-nm radiation falls 0.12 eV short of the energy needed to dissociate O2, large densities of ozone (O3) can be produced from unfocused 248-nm KrF excimer laser irradiation of pure O2. As soon as any O3 is present, it strongly absorbs the 248-nanometer radiation and dissociates to vibrationally excited ground state O2 (among other products), with a quantum yield of 0.1 to 0.15. During the laser pulse, a portion of these molecules absorb a photon and dissociate, which results in the production of three oxygen atoms for one O3 molecule destroyed. Recombination then converts these atoms to O3, and thus O3 production in the system is autocatalytic. A deficiency exists in current models of O3 photochemistry in the upper stratosphere and mesosphere, in that more O3 is found than can be explained. A detailed analysis of the system as it applies to the upper atmosphere is not yet possible, but with reasonable assumptions about O2 vibrational distributions resulting from O3 photodissociation and about relaxation rates of vibrationally excited O2, a case can be made for the importance of including this mechanism in the models.

Slanger, T. G.↗
NASA NTRS1989

Introduction to dissociative recombination

Dissociative recombination (DR) of molecular ions with electrons has important consequences in many areas of physical science. Ab-initio calculations coupled with resonant scattering theory and multichannel quantum defect studies have produced detailed results illuminating the role of ion vibrational excitation, the quantum yields of the DR products, and the role of Rydberg states. The theoretical and experimental results are discussed.

Guberman, Steven L.↗
NASA NTRS1989

Photodissociation of pernitric acid (HO2NO2) at 248 nm

The photodissociation of pernitric acid (PNA) was studied at 248 nm. The quantum yield for production of OH radicals is 34 + or - 16 percent. The yield of OH from PNA was measured relative to that of H2O2. The translational and rotational energy content of the OH photofragment from PNA was characterized. A fluorescent emission was also observed and characterized. It is attributed to electronically excited NO2 produced in the PNA photodissociation. A maximum yield of 30 percent for NO2 production was determined. The intensity of this emission, and a mass spectrometric peak at m/e = 33, were found to be useful means of characterizing the purity of the PNA sample.

Macleod, Helene↗
NASA NTRS1988

CH3O(A-X) fluorescence from photodissociation of dimethyl ether

The paper reports the quantitative photoabsorption and fluorescence cross sections of dimethyl ether (DME) measured with synchrotron radiation. Determinations were also made of the absolute fluorescence cross sections, the fluorescence quantum yield, and the radiative lifetime.

Suto, Masako↗
NASA NTRS1991

Heterogeneous photocatalytic oxidation of atmospheric trace contaminants

The following subject areas are covered: (1) design and construction of continuous flow photoreactor for study of oxidation of trace atmospheric contaminants; (2) establishment of kinetics of acetone oxidation including adsorption equilibration, variation of oxidation rate with acetone concentration and water (inhibitor), and variation of rate and apparent quantum yield with light intensity; (3) exploration of kinetics of butanol oxidation, including rate variation with concentration of butanol, and lack of inhibition by water; and (4) exploration of kinetics of catalyst deactivation during oxidation of butanol, including deactivation rate, influence of dark conditions, and establishment of photocatalytic regeneration of activity in alcohol-free air.

Ollis, David F.↗
NASA NTRS1990

The photochemical origins of life and photoreaction of ferrous ion in the archaean oceans

A general argument is made for the photochemical origins of life. A constant flux of free energy is required to maintain the organized state of matter called life. Solar photons are the unique source of the large amounts of energy probably required to initiate this organization and certainly required for the evolution of life to occur. The completion of this argument will require the experimental determination of suitable photochemical reactions. It is shown that biogenetic porphyrins readily photooxidize substrates and emit hydrogen in the presence of a catalyst. These results are consistent with the Granick hypothesis, which relates a biosynthetic pathway to its evolutionary origin. It has been shown that photoexcitation of ferrous ion at neutral pH with near ultraviolet light produces hydrogen with high quantum yield. This same simple system may reduce carbon dioxide to formaldehyde and further products. These reactions offer a solution to the dilemma confronting the Oparin-Urey-Miller model of the chemical origin of life. If carbon dioxide is the main form of carbon on the primitive earth, the ferrous photoreaction may provide the reduced carbon necessary for the formation of amino acids and other biogenic molecules. These results suggest that this progenitor of modern photosynthesis may have contributed to the chemical origins of life.

Mauzerall, David C.↗