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At least 217 records · Page 12

Reaction of HO2 with O3.

Description of an experiment in which HO2 radicals were produced from the photolysis of O3 at 2537 A in the presence of excess H2 and O2. The O(1 D) atoms produced from the photolysis of O3 react with H2 to produce HO radicals and H atoms. The HO radicals react with H2 to give H2O and more H atoms. All the H atoms then add to O2 to produce HO2 radicals. The quantum yield of O3 removal is measured, and from this measurement the importance of the reaction between HO2 and O3 to yield HO plus 2O2 is determined.

Simonaitis, R.

Photochemistry of planetary atmospheres

The atmospheric composition of Mars is presented, and the applicability of laboratory data on CO2 absorption cross sections and quantum yields of dissociation is discussed. A summary and critical evaluation are presented on the various mechanisms proposed for converting the photodissociation products CO and O2 back to CO2.

Stief, L. J.

Stabilities of nitrogen containing heterocyclic radicals and geometrical influences on non-radiative processes in organic molecules

Theoretical and experimental work on generating radicals by removal of a hydrogen atom from pyrrole, imidazole, indole, and carbazole is reported. Photophysical studies on indolizine and related aza-derivatives show that materials having large S2-S1 energy gaps might exhibit upper state fluorescence. Photodecomposition quantum yields of a series of sterically hindered p-aminobenzene diazonium cations in water were found structurally and wavelength dependent and unquenched in aqueous sodium bromide solutions. Photodecomposition of diazonium materials did not produce a metastable species with a longer lifetime than 1 msec.

Evleth, E. M.

Theoretical and experimental investigation of 'grating' type photovoltaic cells

The fabrication procedure and properties of 'grating' cells made by forming a fine grating pattern of aluminum alloyed into n-silicon wafers are described. The finest grating lines achieved in the cells described were 5 microns; the smallest spacing was about 15 microns. The best temperature for alloying was found to be about 600 C, a bit above the Si-Al eutectic temperature (576 C). The short-circuit current obtained from the best of these cells exposed to 100 mW/sq cm of (simulated air mass zero) illumination was at least equal to that obtained from conventional diffused cells, but their open-circuit voltage was lower. Their quantum yield was strongly blue-shifted; it was flat from 4000 to 8500 A.

Loferski, J. J.

Photochemistry of interstellar molecules

The role of photochemistry in determining the lifetime of interstellar molecules is considered. The probability of photodecomposition depends on three factors, including the absorption cross section, the quantum yield or probability of dissociation following photon absorption, and the interstellar radiation field. A more detailed discussion of the photochemistry of five molecules is presented, giving attention to carbonyl sulfide, methyl acetylene, nitric oxide, acetylene, and benzene. Lifetimes of interstellar molecules in unobscured regions are in the range from 5 to 100 years. It is concluded that polyatomic molecules can exist only in dense clouds which protect them from the full interstellar radiation field.

Stief, L. J.

Vacuum UV photolysis of N2O

Emission from N2 B (3 Pi g) and O(1 S) produced during vacuum UV irradiation of N2O was studied as a function of the wavelength of the incident radiation. Two different processes were responsible for producing N2(B 3 Pi g) close to its production threshold. One process formed B 3 Pi g molecules directly and one indirectly via an unidentified precursor having a lifetime about 27 microsec. The quantum yield of O(1 S) atoms produced by photodissociation of N2O was determined as a function of incident photon energy. This yield is near 100% at 129 nm.

Mcewan, M. J.

Hot hydrogen atoms reactions of interest in molecular evolution and interstellar chemistry

Hot hydrogen atoms which are photochemically generated initiate reactions among mixtures of methane, ethane, water and ammonia, to produce ethanol, organic amines, organic acids, and amino acids. Both ethanol and ethyl amine can also act as substrates for formation of amino acids. The one carbon substrate methane is sufficient as a carbon source to produce amino acids. Typical quantum yields for formation of amino acids are approximately 0.00002 to 0.00004. In one experiment, 6 protein amino acids were identified and 8 nonprotein amino acids verified utilizing gas chromatography-mass spectroscopy. We propose that hot atoms, especially hydrogen, initiate reactions in the thermodynamic nonequilibrium environment of interstellar space as well as in the atmospheres of planets.

Becker, R. S.

O/1 D/ production in ozone photolysis near 3100 A

Relative quantum yields of O(1 D) production in ozone photolysis from 2750 to 3340 A have been determined in the gas phase at -40 C. The O(1 D) was monitored by means of its reaction with isobutane to form isobutyl alcohol. The light source was a high pressure mercury lamp combined with a monochromator, with a bandwidth of 16 A. The results show a constant O(1 D) production below 3000 A, which is taken as unity on the basis of previous work. There is a very sharp fall-off in O(1 D) production which is centered at 3080 A. At 3130 A, O(1 D) production is not greater than 0.1.

Lin, C.-L.

Reactions of CH3, CH3O, and CH3O2 radicals with O3

Ozone was photolyzed at 253.7 nm at 25 and -52 degrees in the presence of CH4 and O2 to measure the reactions of O3 with CH3, CH3O, and CH3O2. The O(1D) atoms produced in the primary photochemical act react with CH4 to give CH3 radicals which in turn can react with O2 to give CH3O2 and CH3O radicals. At very high O2 to O3 concentration ratios, the quantum yield of O3 disappearance approached 1.0, indicating that O3 reactions with CH3O2 and CH3O are slow. Upper limits to the rate coefficients at 25 degrees were computed. At lower values of the concentration ratio, chain decomposition of O3 occurred which could be explained by the reaction of O3 with CH3 radicals to produce CH2O, O2, and H atoms all the time. The two routes to these products are considered, and the preferred reaction channel is found.

Simonaitis, R.

Laboratory observations of the photochemistry of parent molecules: A review

The photochemistry of possible parent molecules of comets has been reviewed. Quantum yields for many of the primary processes are unknown. Energy partitioning among the fragments has not been extensively investigated. A few of the studies have been performed as a function of the number of collisions that the excited molecules undergo, so that possible differences that may occur in a cometary environment may be ascertained.

Jackson, W. M.

Particles, environments and possible ecologies in the Jovian atmosphere

The eddy diffusion coefficient is estimated as a function of altitude, separately for the Jovian troposphere and mesosphere. Complex organic molecules produced by the Ly alpha photolysis of methane may possibly be the absorbers in the lower mesosphere which account for the low reflectivity of Jupiter in the near ultraviolet. The optical frequency chromophores are localized at or just below the Jovian tropopause. Candidate chromophore molecules must satisfy the condition that they are produced sufficiently rapidly that convective pyrolysis maintains the observed chromophore optical depth. The condition is satisfied if complex organic chromophores are produced with high quantum yield by NH3 photolysis at less than 2,300 A. Jovian photoautotrophs in the upper troposphere satisfy this condition well, even with fast circulation, assuming only biochemical properties of comparable terrestrial organisms. An organism in the form of a thin, gas filled balloon can grow fast enough to replicate if (1) it can survive at the low mesospheric temperatures, or if (2) photosynthesis occurs in the troposphere.

Sagan, C.

Exciton coupling in molecular crystals

The implications of perfect exciton coupling and molecular vibrations were investigated, as well as the effect they have on the lifetime of singlet and triplet excitons coupled in a limiting geometry. Crystalline bibenzyl, Cl4Hl4, provided a situation in which these mechanisms involving exciton coupling can be studied in the limit of perfect coupling between units due to the crystal's geometry. This geometry leads to a coupling between the two halves of the molecule resulting in a splitting of the molecular excited states. The study reported involves an experimental spectroscopic approach and begins with the purification of the bibenzyl. The principal experimental apparatus was an emission spectrometer. A closed cycle cryogenic system was used to vary the temperature of the sample between 20 K and 300 K. The desired results are the temperature-dependent emission spectra of the bibenzyl; in addition, the lifetimes and quantum yields measured at each temperature reveal the effect of competing radiationless processes.

Ake, R. L.

Ultraviolet response of semitransparent multialkali photocathodes

The UV spectral sensitivity of two semitransparent visible sensitive photocathodes for spaceborne applications, a trialkali, Cs-Na2KSB, and a bialkali, K2CsSb, both on MgF2 substrates. Results show that for extended wavelength coverage, the bialkali photocathode affords increased quantum yield as compared with the trialkali type, and that the latter has a more variable responsivity with wavelength.

Sobieski, S.

Laboratory measurements

A compilation of chemical and photochemical data that are relevant to stratospheric modeling is presented. There are three broad categories of data: (1) rate constants for chemical reactions, including temperature and pressure dependencies along with product distributions; (2) absorption cross sections, photodissociation quantum yield, and photolysis; (3) heterogeneous chemical processes.

Source record

A reexamination of the photochemistry of the Cl2-O3 system

An analysis is conducted of experimental data reported by Norrish and Neville (1934) who studied quantum yields for ozone destruction. A reaction scheme is presented for the Cl2-O3 system. It is demonstrated that the reaction scheme provides a quantitative explanation concerning the main features of the experimental data. Attention is given to reactions involving ClO, OClO, ClOO, and ClO3.

Rundel, R. D.

Hydrogen from the solar photolysis of water

Developments related to the study of photosynthesis are examined and aspects of photosensitization by solids are considered. It is pointed out that solids photosensitization for solar photochemical fuel formation is now an extremely active research area as a consequence of the promising results obtained with semiconductor photoelectrodes. The investigation of water decomposition schemes involving heterogeneous reactions is likely to be a productive area. As is the case for photosynthesis, the known examples of water decomposition by solids photosensitization involve charge separation processes immediately following light absorption. Homogeneous photoredox reactions are also discussed, taking into account thermochemical and photochemical cycles leading to the formation of a photooxidized ion, hydrogen quantum yields in the photo-oxidation aqueous ions, and thermochemical and photochemical cycles leading to the formation of a photoreduced ion.

Ryason, P. R.

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.

Design, fabrication, and delivery of a charge injection device as a stellar tracking device

Six 128 x 128 CID imagers fabricated on bulk silicon and with thin polysilicon upper-level electrodes were tested in a star tracking mode. Noise and spectral response were measured as a function of temperature over the range of +25 C to -40 C. Noise at 0 C and below was less than 40 rms carriers/pixel for all devices at an effective noise bandwidth of 150 Hz. Quantum yield for all devices averaged 40% from 0.4 to 1.0 microns with no measurable temperature dependence. Extrapolating from these performance parameters to those of a large (400 x 400) array and accounting for design and processing improvements, indicates that the larger array would show a further improvement in noise performance -- on the order of 25 carriers. A preliminary evaluation of the projected performance of the 400 x 400 array and a representative set of star sensor requirements indicates that the CID has excellent potential as a stellar tracking device.

Burke, H. K.