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At least 73 records · Page 4
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NASA NTRS1971

Photochemistry of interstellar molecules

The photochemistry of two diatomic and eight polyatomic molecules is discussed quantitatively. For an interstellar molecule, the lifetime against photodecomposition depends upon the absorption cross section, the quantum yield or probability of dissociation following photon absorption, and the interstellar radiation field. The constant energy density of Habing is used for the unobserved regions of interstellar radiation field, and the field in obscuring clouds is estimated by combining the constant flux with the observed interstellar extinction curve covering the visible and ultraviolet regions. Lifetimes against photodecomposition in the unobscured regions and as a function of increasing optical thickness in obscuring clouds are calculated for the ten species. The results show that, except for CO, all the molecules have comparable lifetimes of less than one hundred years. Thus they can exist only in dense clouds and can never have been exposed to the unobscured radiation. The calculations further show that the lifetimes in clouds of moderate opacity are of the order of one million years.

Stief, L. J.↗
NASA NTRS1972

Photochemistry and lifetimes of interstellar molecules.

Quantitative discussion of the photochemistry and lifetime against photodecomposition of five interstellar molecules: H2CO, NH3, H2O, CH4, and CO. For the first four molecules, primary photochemical decomposition processes yielding atomic and molecular hydrogen are considered in addition to photoionization. The quantum yield for decomposition of these molecules is unity. For CO, only decomposition to ground-state carbon and oxygen atoms occur, but the quantum yield is not known and may be considerably less than unity. The radiation field in obscuring clouds is estimated, using an interstellar extinction curve for the Perseus region.

Stief, L. J.↗
NASA NTRS1976

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.↗
NASA NTRS1975

Fluorine photochemistry in the stratosphere

The photochemistry of fluorine in the stratosphere is surveyed in order to estimate the effect on ozone of fluorine atoms released by the breakdown of chlorofluoromethanes. The catalytic efficiency for ozone destruction by fluorine is found to be less than .0001 that of chlorine in the altitude range from 25 to 50 km.

Stolarski, R. S.↗
NASA NTRS1976

The photochemistry of ammonia in the Jovian atmosphere

A reinvestigation of the ammonia photochemistry in the Jovian lower atmosphere above the cloud tops is conducted in connection with certain questions concerning the model proposed by Strobel (1973). Chemical reactions and their rate coefficients are considered along with the model atmosphere, solar fluxes, the continuity equations, and numerical details. Differences between the newmodel and Strobel's model are related to more moderate ammonia depletion relations. The height profiles of H, NH2, N2H3, N2H4, and NH3 concentrations are presented in a graph.

Prasad, S. S.↗
NASA NTRS1977

Photochemistry of nitrogen in the Martian atmosphere

Models are developed for the photochemistry of a CO2-H2O-N2 atmosphere on Mars. Estimates are given for the concentrations of N, NO, NO2, NO3, N2O5, HNO2, HNO3, and N2O as a function of altitude. Nitric oxide is the most abundant form of odd nitrogen, present with a mixing ratio relative to CO2 of the order of 1 hundred-millionth. Deposition rates for nitrite and nitrate minerals could be as large as 300,000 N equivalent atoms per sq cm/sec under present conditions and may have been higher in the past.

Yung, Y. L.↗
NASA NTRS1977

Photochemistry of tropospheric ozone

A photochemical equilibrium model of minor constituent chemistry in the troposphere was constructed to investigate the photochemistry of tropospheric ozone. We find that photochemical production must be supplemented by additional sources to account for observed ozone levels in clean air, while photochemical loss is more important than surface destruction as an ozone loss mechanism. Photochemically produced ozone is sensitive to the NO(x) background in the model, exhibiting a maximum of about 0.5 ppb of NO(x).

Stewart, R. W.↗
NASA NTRS1977

A computationally fast one-dimensional diffusion-photochemistry model of SST wakes

A computational technique applicable to analysis of supersonic transport (SST) wake photochemistry and diffusion is presented. Sensitivity studies of SST effluent effects upon ozone depletion are facilitated by the computational rapidity of the method. The article compares results from other studies and predictions of some variables related to global NOx input. Results indicate that the NO/NO2 ratio in an SST wake at photochemical equilibrium is a sensitive function of photolysis rates.

Matloff, G. L.↗
NASA NTRS1978

The uncertainty in ozone calculations by a stratospheric photochemistry model

At present, there is an apparent conflict between one-dimensional stratospheric photochemistry models used in predicting ozone depletion and average data for stratospheric ozone. This conflict is in three particulars - column density of O3 and ozone density in the regions around 30 km and 50 km altitude. A study of the sensitivity of one such model to the values of reaction rates, boundary conditions, solar intensities, photolysis cross sections, and O(1D) yield parameters reveals that even at the 2-sigma uncertainty limit due to these input parameters, the model does not overlap the data for O3 density at 30 km and 50 km. The data is outside the 1-sigma model uncertainty limit for O3 column density. The study also shows the relative contribution of the various parameters studied to the imprecision in these model results.

Butler, D. M.↗
NASA NTRS1979

The photochemistry of N/+/ ions

The photochemistry of N(+) ions in the daytime thermosphere is studied using the data base of the Atmosphere Explorer C Satellite. The reaction O(+) + N(2D) yields O + N(+) is considered a major source of N(+) ions at altitudes between 250 and 500 km. At altitudes below 300 km, N(+) is removed by reactions with O2, but at higher altitudes the reactions of N(+) with O and with H are the most important loss mechanisms. The empirical rate coefficients for reactions N(+) + O yields N and O(+) and N(+) + H yields N + H(+) are derived.

Constantinides, E. R.↗
NASA NTRS1981

Photochemistry of acetylene at 1470 A

The considered study was conducted to assess the importance of the major primary photochemical process of acetylene at 1470 A, to clarify the role of the metastable excited state, and to obtain information on the rates of C2H reactions with H2 and CH4. Concerning the photodissociation process of acetylene, it was found that at acetylene pressures below 0.8 Torr the direct dissociation process (C2H2 yields C2H + H) is the most important primary photochemical process with a quantum yield of 0.3. Another primary process may be the production of H2 with a quantum yield of approximately 0.1 (C2H2 yields C2 + H2). At acetylene pressures above 0.8 Torr diacetylene is formed by the direct dissociation process followed by the reaction: C2H + C2H2 yields C4H2 + H. At pressures above 20 Torr benzene becomes an important product with a concomitant decrease of diacetylene. The role of acetylene in the photochemistry of the Jovian atmosphere is also considered

Okabe, H.↗
NASA NTRS1982

The photochemistry of carbon-rich circumstellar shells

The effect of ambient ultraviolet photons on the chemical structure of carbon-rich, circumstellar envelopes is investigated with a simple formulation of the time-dependent, photochemical rate equations valid for optically thick shells. Molecules injected into the shielded inner envelope are broken down when they reach the outer regions where ambient ultraviolet photons can penetrate. A quantitative description of the abundance variations is obtained for the case of uniform expansion by detailed consideration of the shielding of the radiation by the dust and molecules of the envelope. Representative results are presented to illustrate the role of shielding in defining the extent of molecular envelopes, the formation of C I and C II shells by photodestruction of carbon-bearing molecules, and the development of layered chemical structures from the photobreakup of polyatomic molecules. Photochemistry makes the outer parts of thick, carbon-rich envelopes into complex regions containing radicals, ions, and atoms which are of considerable observational and theoretical interest.

Huggins, P. J.↗
NASA NTRS1981

Photochemistry in planetary atmospheres

Widely varying paths of evolutionary history, atmospheric processes, solar fluxes, and temperatures have produced vastly different planetary atmospheres. The similarities and differences between the earth atmosphere and those of the terrestrial planets (Venus and Mars) and of the Jovian planets are discussed in detail; consideration is also given to the photochemistry of Saturn, Uranus, Pluto, Neptune, Titan, and Triton. Changes in the earth's ancient atmosphere are described, and problems of interest in the earth's present troposphere are discussed, including the down wind effect, plume interactions, aerosol nucleation and growth, acid rain, and the fate of terpenes. Temperature fluctuations in the four principal layers of the earth's atmosphere, predicted decreases in the ozone concentration as a function of time, and spectra of particles in the earth's upper atmosphere are also presented. Finally, the vertical structure of the Venus cloud system and the thermal structure of the Jovian planets are shown graphically.

Levine, J. S.↗
NASA NTRS1982

The photochemistry of the paleoatmosphere

Recent progress in the understanding of the chemistry and photochemistry of the paleoatmosphere is reviewed with emphasis on the application of photochemical models to the investigation of the evolution of the atmosphere. Photochemical calculations are presented which show that a primordial highly reducing atmosphere composed of methane and ammonia, if it formed at all, would be short-lived in the presence of solar ultraviolet radiation, giving way rapidly to a more mildly reducing atmosphere of carbon dioxide and nitrogen. Estimations of O2 produced from the photolysis of water vapor prior to the emergence of photosynthesis range from less than 10 to the -14th to 0.1 times the present atmospheric level, indicating the need for further research. A series of photochemical models of increasing complexity has been developed to study the evolution of atmospheric ozone taking into account reactions with O atoms, hydrogen oxides, nitrogen oxides, and chlorine as well as vertical transport, temperature and tropospheric chemistry so that the total content and vertical distribution of O3 may be determined for a specified level of paleoatmospheric O2.

Levine, J. S.↗
NASA NTRS1983

On the relationship between the greenhouse effect, atmospheric photochemistry, and species distribution

The coupling that exists between infrared opacity changes and tropospheric (and to a lesser extent stratospheric) chemistry is explored in considerable detail, and the effects arising from various perturbations are examined. The studies are carried out with a fully coupled one-dimensional radiative-convective-photochemical model (RCP) that extends from the surface to 53.5 km and has the capability of calculating surface temperature changes due to both chemical and radiative perturbations. The model encompasses contemporary atmospheric chemistry and photochemistry involving the O(x), HO(x), NO(x), and Cl(x) species.

Callis, L. B.↗
NASA NTRS1983

Photochemistry of N2(+) in the daytime F region

The photochemistry of N2(+) in the daytime F region continues to be a source of concern due primarily to the uncertain roles of the metastable O+(2D) ion and possible vibrational excitation. This investigation adopts a unique subset of data from the Atmospheric Explorer C satellite that spans distinct regions near the low-latitude F peak wherein either chemical reactions or electron processes alternatively control the N2(+) abundances. Concentrations of N2(+) calculated according to current theory and including recent laboratory data for O+(2D) losses via N2 are found to exceed ionospheric observations between 220 and 400 km by a factor near 2. Relevant characteristics of the basic molecular ion concentration measurements are described, along with an analysis for select orbits conducted according to current photochemical equilibrium theory. Possible simple modifications of this theory are discussed in terms of the constraints suggested by the nature of the observations.

Breig, E. L.↗
NASA NTRS1983

The young sun and the atmosphere and photochemistry of the early earth

The origin and evolution of the earth's early atmosphere depend crucially on the dissipation time of the primitive solar nebula (SN). Using different theories of turbulence, the dissipation time of an SN of 0.1 solar mass is estimated as 2.5-8.3 Myr. Because accretion times are usually much longer, it is concluded that most planetary accretion must have occurred in a gas-free environment. Using new IUE data, a wavelength-dependent UV flux is constructed for the young sun which is then used to study the photochemistry and concentrations of O, O2, O3, OH, H, HCO and formaldehyde H2CO in the earth's early prebiological atmosphere.

Canuto, V. M.↗
NASA NTRS1984

The photochemistry of a remote marine stratiform cloud

The coupled gas- and aqueous-phase photochemistry of a stratiform cloud in a remote region of the marine atmosphere is investigated with a time-dependent box model. Both scavenging of ambient acidic aerosols and gases as well as aqueous-phase chemical reactions within droplets are found to be important sources of acidity to cloud water and can lead to pH levels in cloud water in the remote marine atmosphere well below 5.6. The major sources of acidity via aqueous-phase chemical reactions are the generation of sulfuric acid from dissolved SO2 and the generation of formic acid from dissolved formaldehyde. In both cases, aqueous-phase free radicals can play a significant role either directly by oxidizing dissolved SO2 and HCHO or indirectly by producing the aqueous-phase oxidant H2O2. The rate of SO2 conversion to sulfuric acid is sensitive to a variety of parameters including the accommodation or sticking coefficient for SO2, H2O2, HO2, and OH, the liquid water content, and the ambient levels of SO2, HNO3, and other acidic or basic gases. Because high levels of SO2 tend to deplete cloud water of H2O3, the possibility exists that the pH of precipitation in polluted regions will respond nonlinearly to reduced SO2 emissions.

Chameides, W. L.↗