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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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Deuterium enrichment of polycyclic aromatic hydrocarbons by photochemically induced exchange with deuterium-rich cosmic ices

The polycyclic aromatic hydrocarbon (PAH) coronene (C24H12) frozen in D2O ice in a ratio of less than 1 part in 500 rapidly exchanges its hydrogen atoms with the deuterium in the ice at interstellar temperatures and pressures when exposed to ultraviolet radiation. Exchange occurs via three different chemical processes: D atom addition, D atom exchange at oxidized edge sites, and D atom exchange at aromatic edge sites. Observed exchange rates for coronene (C24H12)-D2O and d12-coronene (C24D12)-H2O isotopic substitution experiments show that PAHs in interstellar ices could easily attain the D/H levels observed in meteorites. These results may have important consequences for the abundance of deuterium observed in aromatic materials in the interstellar medium and in meteorites. These exchange mechanisms produce deuteration in characteristic molecular locations on the PAHs that may distinguish them from previously postulated processes for D enrichment of PAHs.

NASA Center ARC↗

Sulfur and nitrogen reactions for cometary comae ion chemistry

The low pressure reactions of sulfur dioxide, carbon disulfide, and hydrazine with H2O+ and H3O+ were studied by the ion cyclotron resonance technique. These reactions are potentially important for sulphur chemistry in cometary comae. Rate coefficients and branching ratios of product channels are presented.

NASA Center JPL↗

UV irradiation of polycyclic aromatic hydrocarbons in ices: production of alcohols, quinones, and ethers

Polycyclic aromatic hydrocarbons (PAHs) in water ice were exposed to ultraviolet (UV) radiation under astrophysical conditions, and the products were analyzed by infrared spectroscopy and mass spectrometry. Peripheral carbon atoms were oxidized, producing aromatic alcohols, ketones, and ethers, and reduced, producing partially hydrogenated aromatic hydrocarbons, molecules that account for the interstellar 3.4-micrometer emission feature. These classes of compounds are all present in carbonaceous meteorites. Hydrogen and deuterium atoms exchange readily between the PAHs and the ice, which may explain the deuterium enrichments found in certain meteoritic molecules. This work has important implications for extraterrestrial organics in biogenesis.

NASA Center ARC↗

Structure and dynamics of amorphous water ice

Further insight into the structure and dynamics of amorphous water ice, at low temperatures, was obtained by trapping in it Ar, Ne, H2, and D2. Ballistic water-vapor deposition results in the growth of smooth, approximately 1 x 0.2 micrometer2, ice needles. The amorphous ice seems to exist in at least two separate forms, at T < 85 K and at 85 < T < 136.8 K, and transform irreversibly from one form to the other through a series of temperature-dependent metastable states. The channels formed by the water hexagons in the ice are wide enough to allow the free penetration of H2 and D2 into the ice matrix even in the relatively compact cubic ice, resulting in H2-(D2-) to-ice ratios (by number) as high as 0.63. The larger Ar atoms can penetrate only into the wider channels of amorphous ice, and Ne is an intermediate case. Dynamic percolation behavior explains the emergence of Ar and Ne (but not H2 and D2) for the ice, upon warming, in small and big gas jets. The big jets, each containing approximately 5 x 10(10) atoms, break and propel the ice needles. Dynamic percolation also explains the collapse of the ice matrix under bombardment by Ar , at a pressure exceeding 2.6 dyn cm-2, and the burial of huge amounts of gas inside the collapsed matrix, up to an Ar-to-ice of 3.3 (by number). The experimental results could be relevant to comets, icy satellites, and icy grain mantles in dense interstellar clouds.

NASA Program Exobiology↗

Stable light isotope biogeochemistry of hydrothermal systems

The stable isotopic composition of the elements O, H, S and C in minerals and other chemical species can indicate the existence, extent, conditions and the processes (including biological activity) of hydrothermal systems. Hydrothermal alteration of the 18O/16O and D/H values of minerals can be used to detect fossil systems and delineate their areal extent. Water-rock interactions create isotopic signatures which indicate fluid composition, temperature, water-rock ratios, etc. The 18O/16O values of silica and carbonate deposits tend to increase with declining temperature and thus help to map thermal gradients. Measurements of D/H values can help to decipher the origin(s) of hydrothermal fluids. The 34S/32S and 13C/12C values of fluids and minerals reflect the origin of the S and C as well as oxygen fugacities and key redox processes. For example, a wide range of 34S/32S values which are consistent with equilibration below 100 degrees C between sulfide and sulfate can be attributed to sulfur metabolizing bacteria. Depending on its magnitude, the difference in the 13C/12C value of CO2 and carbonates versus organic carbon might be attributed either to equilibrium at hydrothermal temperatures or, if the difference exceeds 1% (10/1000), to organic biosynthesis. Along the thermal gradients of thermal spring outflows, the 13C/12C value of carbonates and 13C-depleted microbial organic carbon increases, principally due to the outgassing of relatively 13C-depleted CO2.

Review, Tutorial↗

High-resolution spectroscopy of H2SO4, HDSO4, and D2SO4 vapor in the region 1200-10,000 cm(-1)

The high-resolution (0.05 cm(-1)) spectra of gas-phase H2SO4, HDSO4, and D2SO4 were measured over the frequency region 1200-10,000 cm(-1) using Fourier-transform infrared spectroscopy. The increased resolution of this work compared with previous studies has lead to an improved vibrational analysis of H2SO4. This study has answered unresolved questions about combination bands and overlapping features from previous gas-phase spectroscopic studies of H2SO4 and marks the first experimental measurement of the nu8 and nu15 torsional vibrations in this molecule. This work leads to a brief discussion on vibrational mode mixing in sulfuric acid.

Deuterium/chemistry↗