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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 109 records · Page 6

On the Relationship of Multiple Solutions in Tropospheric Photochemistry to Observable Phenomena

Multiple steady-state solutions are a fairly robust feature of simplified models of tropospheric photochemistry and have been reported for a range of different modeling assumptions. Multiple solutions occur through a bifurcation as changes in a control parameter induce a transition from low to high NO(x) conditions. The usual control parameters are the sources of NO and of CO, CH4 or non-methane hydrocarbons. Typically, with increasing NO source, bifurcations occur at NO(x). concentrations that are higher than would be expected of even heavily polluted conditions. However, there are other ways of inducing a low NO(x) - high NO(x) transition. In this paper the primary control parameter is solar zenith angle. This is varied throughout the year by computing noontime steady states on successive days. Background NO(x), varied by assuming different NO(x) sources values, is used as a secondary control parameter. It is found that bifurcations can occur from high to low NO(x) conditions, for reasonable background NO(x) levels, as the model progresses through spring and then from low to high NO,, during the progression through fall. A time dependent version of this model has been run for the same parameter values as in the steady state runs. This shows rapid spring and fall transitions between high and low NO(x) states. H2O2, for example, rises from sub-ppb levels to about 2 ppb over a five day period in spring and declines quickly, but less precipitously, in fall. This study supports the suggestions that the rapid change in peroxide concentrations between summer and winter conditions may be understood as a manifestation of different underlying steady-state behavior.

Stewart, Richard W.↗

The 2140 cm(exp -1) (4.673 Microns) Solid CO Band: The Case for Interstellar O2 and N2 and the Photochemistry of Non-Polar Interstellar Ice Analogs

The infrared spectra of CO frozen in non-polar ices containing N2, CO2, O2, and H2O, and the ultraviolet photochemistry of these interstellar/precometary ice analogs are reported. The spectra are used to test the hypothesis that the narrow 2140/cm (4.673 micrometer) interstellar absorption feature attributed to solid CO might be produced by CO frozen in ices containing non-polar species such as N2 and O2. It is shown that mixed molecular ices containing CO, N2, O2, and CO2 provide a very good match to the interstellar band at all temperatures between 12 and 30 K both before and after photolysis. The optical constants (real and imaginary parts of the index of refraction) in the region of the solid CO feature are reported for several of these ices.

Elsila, Jamie↗

Mars Photochemistry: Weak Points and Search for Solutions

Photochemical modeling is a powerful tool to study the chemical composition of a planetary atmosphere. Using densities of just two or three species near the surface of a planet, photochemistry makes it possible to calculate vertical density profiles for a few dozen species and describe chemical and physical processes that determine these profiles.

Vladimir A Krasnopolsky↗

Atmospheric Photochemistry

The upper atmosphere offers a vast photochemical laboratory free from solid surfaces, so all reactions take place in the gaseous phase. At 30 km altitude the pressure has fallen to about one-hundredth of that at ground level, and we shall, rather arbitrarily, regard the upper atmosphere as beginning at that height. By a little less than 100 km the pressure has fallen to 10(exp -3) mm Hg and is decreasing by a power of ten for every 15 km increase in altitude. Essentially we are concerned then with the photochemistry of a nitrogen-oxygen mixture under low-pressure conditions in which photo-ionization, as well as photodissociation, plays an important part. Account must also be taken of the presence of rare constituents, such as water vapour and its decomposition products, including particularly hydroxyl, oxides of carbon, methane and, strangely enough, sodium, lithium and calcium. Many curious and unfamiliar reactions occur in the upper atmosphere. Some of them are luminescent, causing the atmosphere to emit a dim light called the airglow. Others, between gaseous ions and neutral molecules, are almost a complete mystery at this time. Similar interesting phenomena must occur in other planetary atmospheres, and they might be predicted if sufficient chemical information were available.

Massey, Harrie↗

Photochemistry of porphyrins: a model for the origin of photosynthesis

A series of porphyrins and catalysts has been prepared as a model for the origin of photosynthesis on the primordial earth. These compounds have been used to test the hypotheses that (1) the biosynthetic pathway to chlorophyll recapitulates the evolutionary history of photosynthesis, and (2) the proto-photosythetic function of biogenetic porphyrins (biosynthetic chlorophyll precursors) was the oxidation of organic molecules by photoexcited porphyrins with the attendant emission of molecular hydrogen. This paper describes experiments in which photoexcited biogenetic porphyrins oxidize ethylenediamine tetraacetic acid (EDTA). The concomitant reduction of protons to hydrogen gas occurs in the presence of a colloidal platinum catalyst. The addition of methyl viologen, a one-electron shuttle, increases the amount of molecular hydrogen generated during long irradiations and the quantum yield of hydrogen production. When the porphyrin and catalyst are held in association by molecular complexes, the increased efficiency of electron transfer produces higher yields of hydrogen gas.

Hydrogen/chemistry↗

Current State of Modeling the Photochemistry of Titan's Mutually Dependent Atmosphere and Ionosphere

In the context of recent observations, microphysical models, and laboratory data, a photochemical model of Titan's atmosphere, including updated chemistry focusing on rate coefficients and cross sections measured under appropriate conditions, has been developed to increase understanding of these processes and improve upon previous Titan photochemical models. The model employs a two-stream discrete ordinates method to characterize the transfer of solar radiation, and the effects of electron-impact, cosmic-ray deposition, and aerosol opacities from fractal and Mie particles are analyzed. Sensitivity studies demonstrate that an eddy diffusion profile with a homopause level of 850 km and a methane stratospheric mole fraction of 2.2% provides the best fit of stratospheric and upper atmosphere observations and an improved fit over previous Titan photochemical models. Lack of fits for C3H8, HC3N, and possibly C2H3CN can be resolved with adjustments in aerosol opacity. The model presents a benzene profile consistent with its detection in Titan's stratosphere [Coustenis et al., 2003], which may play an important role in the formation of Titan hazes. An electron peak concentration of 4200 cm(exp -3) is calculated, which exceeds observations by 20%, considerably lower than previous ionosphere models. With adjustments in aerosol opacities and surface fluxes the model illustrates that reasonable fits to existing observations are possible with a single eddy diffusion profile, contrary to the conclusions of previous Titan models. These results will aid in the receipt and interpretation of data from Cassini-Huygens, which will arrive at Titan in 2004 and deploy a probe into Titan's atmosphere in January 2005.

ion chemistry↗

The Photochemistry of Pyrimidine in Pure H2O Ice Subjected to Different Radiation Environments and the Formation of Uracil

Nucleobases are N-heterocycles which are the informational subunits of DNA and RNA. They include pyrimidine bases (uracil, cytosine, and thymine) and purine bases (adenine and guanine). Nucleobases have been detected in several meteorites, although no Nheterocycles have been observed in space to data. Laboratory experiments showed that the ultraviolet (UV) irradiation of pyrimidine in pure H2O ice at low temperature (<=20 K) leads to the formation of pyrimidine derivatives including the nucleobase uracil and its precursor 4(3H)-pyrimidone. These results were confirmed by quantum chemical calculations. When pyrimidine is mixed with combinations of H2O, NH3, CH3OH, and CH4 ices under similar conditions, uracil and cytosine are formed. In the present work we study the formation of 4(3H)-pyrimidone and uracil from the irradiation of pyrimidine in H2O ice with high-energy UV photons (Lyman , He I, and He II lines) provided by a synchrotron source. The photo-destruction of pyrimidine in these H2O ices as well as the formation yields for 4(3H)-pyrimidone and uracil are compared with our previous results in order to study the photo-stability of pyrimidine and the production efficiency of uracil as a function of the photon energy.

Radiation↗