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At least 199 records · Page 11

Branching ratios in the N + CH3 reaction - Formation of the methylene amidogen (H2CN) radical

The discharge-flow mass spectrometer system described by Brunning and Stief (1986) and Nejad et al. (1988) is used to determine the branching ratios for the reaction N + CH3. The results are presented in extensive tables and graphs and characterized in detail, and the implications for HCN formation in the atmosphere of Titan are considered. It is found that the main reaction channel at room temperature is H2CN + H, with about 10 percent giving HCN + H2; no isotope effects are seen when CH3 is replaced with CD3, and the branching ratios appear to be temperature-independent.

Marston, G.↗

Was adenine the first purine?

Oligomerization of HCN (1 molar) in the presence of added formaldehyde (0.5 molar) produced an order of magnitude more 8-hydroxymethyladenine than adenine or any other biologically significant purine. This result suggests that on the prebiotic earth, nucleoside analogs may have been synthesized directly in more complex mixtures of HCN with other aldehydes.

Schwartz, Alan W.↗

Infrared aircraft measurements of stratospheric composition over Antarctica during September 1987

The Jet Propulsion Laboratory Mark IV interferometer recorded high-resolution, infrared solar spectra from the NASA DC-8 aircraft during flights over Antarctica in September 1987. The atmospheric absorption features in these spectra have been analyzed to determine the burdens of O3, NO, NO2, HNO3, ClNO3, HCl, HF, CO2, CH4, N2O, HCN, CO, H2O, CFCl3, and CF2Cl2. The results show a 'collar' of high HNO3 and ClNO3 surrounding a 'core' in which the burdens of these and of HCl and NO2 are very low. Clear increases in the burdens of HF and HNO3 were observed during the course of September in the vortex core. HCl and NO2 exhibited smaller, less significant increases. The burdens of the tropospheric source gases, N2O, CH4, HCN, CFCl3, CF2Cl2, CO, and H2O, were observed to be much smaller over Antarctica than at midlatitudes. This, together with the fact that HF over Antarctica was more than double its midlatidue value, suggests that downwelling had occurred.

Toon, G. C.↗

Structural isomers of C2N(+) - A selected-ion flow tube study

Reactivities of the structural isomers CCN(+) and CNC(+) were examined in a selected-ion flow tube at 300 + or - 5 K. The less reactive CNC(+) isomer was identified as the product of the reactions of C(+) + HCN and C(+) + C2N2; in these reactions only CNC(+) can be produced because of energy constraints. Rate coefficients and branching ratios are reported for the reactions of each isomer with H2, CH4, NH3, H2O, C2H2, HCN, N2, O2, N2O, and CO2. Ab initio calculations are presented for CCN(+) and CNC(+); a saddle point for the reaction CCN(+) yielding CNC(+) is calculated to be 195 kJ/mol above CNC(+). The results provide evidence that the more reactive CCN(+) isomer is unlikely to be present in measurable densities in interstellar clouds.

Knight, J. S.↗

Dense gas and HII regions in the starburst galaxy NGC 253

The energetic activity in the nuclear barred region of NGC 253 is attributable to a burst of star formation. NGC 253 is in many ways a twin of the prototypical starburst galaxy M82; the strong non-thermal radio continuum, high far-infrared luminosity, and bright molecular emission of the central 1 Kpc parallel the morphology of the M82 starburst. Furthermore, the filamentary low ionization optical emission and extended x ray emission along the minor axis in NGC 253 is similar to a scaled down version of the well developed galactic bipolar wind in M82. The infrared luminosity of NGC 253, 3(exp 10) solar luminosity, is comparable to M82 but is emitted from a smaller region (Telesco and Harper 1980). This suggests that the NGC 253 starburst may be more intense and at an earlier evolutionary stage than M82. However, the presence of a non-stellar AGN in NGC 253 may complicate the comparison (Turner and Ho, 1985). Researchers used the Hat Creek millimeter interferometer to map emission from the J = 1 to 0 transitions of HCN and HCO(+) as well as 3 mm continuum emission, toward the nuclear region of NGC 253. The HCO(+) and continuum observations are sensitive to spatial scales from 6 to 45 seconds. The 2 minute field of view comfortably includes the entire starburst region (about 40 seconds; 650 pc). Because the longer baseline HCN observations are not yet complete, they are only sensitive to spatial scales from 15 to 45 seconds.

Carlstrom, J. E.↗

Spatial variation of the physical conditions of molecular gas in galaxies

Multi-line studies of CO-12, CO-13, C-18O, HCN, and HCO(+) at 3 mm, 1.3 mm, and 0.8 mm using the Institute for Radio Astronomy in the Millimeter range (IRAM) 30 m telescope, with the IRAM superconductor insulator superconductor (SIS) receivers and the Max Planck Institute for External Physics (MPE) 350 GHz SIS receiver, show that the densities and temperatures of molecular gas in external galaxies change significantly with position. CO-12 measures the densities and temperature of diffuse interclump molecular gas, but not the bulk of the molecular gas. Simple one-component models, with or without external heating, cannot account for the weakness of the CO-12 J = 3 to 2 line relative to J = 2 to 1 and J = 1 to 0. CO-12 does not trace the bulk of the molecular gas, and optical depth effects obviate a straightforward interpretation of CO-12 data. Instead, researchers turned to the optically thin CO isotopes and other molecular species. Isotopic CO lines measure the bulk of the molecular gas, and HCN and HCO(+) pick out denser regions. Researchers find a warm ridge of gas in IC 342 (Eckart et al. 1989), denser gas in the starburst nucleus of IC 342, and a possible hot-spot in NGC 2903. In IC 342, NGC 2146, and NGC 6764, the CO-13 J = 2 to 1 line is subthermally populated, implying gas densities less than or equal to 10(exp 4) cm(-3).

Jackson, James M.↗

Millimetre observations of comets P/Brorsen-Metcalf (1989o) and Austin (1989c1) with the IRAM 30-m radio telescope

Millimeter observations with the IRAM 30 m telescope were conducted in comet P/Brorsen-Metcalf (1989o) on September 1989 and Austin (1989c1) on April and May 1990. The HCN J(1-0) and J(3-2) lines were detected in both comets. The HCN production rate relative to water in P/Brorsen-Metcalf is comparable to that previously measured in comet P/Halley, while that inferred in comet Austin might be smaller by a factor of two. The H2CO(3 sub 12 - 2 sub 11) transition, marginally observed in comet P/Brorsen-Metcalf, was firmly detected in May 1990 in comet Austin. Observations performed at offset positions suggest that the source of H2CO might be distributed. The H2CO abundance is on the order of 0.5 percent that of water for both comets, assuming a scalelength of 10(exp 4) km at 1 AU from the Sun for the distributed source. During the May observing period of comet Austin, two new species were detected for the first time in a comet: hydrogen sulfide (H2S) through its 1(sub 10) - 1(sub 01) ortho line at 169 GHz, and methanol (CH3OH) through J(3-2) delta K = 0 transitions at 145 GHz. Preliminary estimates of their abundances are 1.5 x 10(exp -3) for H2S and 8 x 10(exp -3) for CH3OH.

Colom, P.↗

Production of organic compounds in plasmas: A comparison among electric sparks, laser-induced plasmas and UV light

In order to study the production of organic compounds in plasmas (and shocks), various mixtures of N2, CH4, and H2, modeling the atmosphere of Titan, were exposed to discrete sparks, laser-induced plasmas (LIP) and ultraviolet light. The yields of HCN and simple hydrocarbons were measured and compared to those calculated from a simple quenched thermodynamic equilibrium model. The agreement between experiment and theory was fair for HCN and C2H2. However, the yields of C2H6 and other hydrocarbons were much higher than those predicted by the model. Our experiments suggest that photolysis by ultraviolet light from the plasma is an important process in the synthesis. This was confirmed by the photolysis of gas samples exposed to the light, but not to the plasma or shock waves. The results of these experiments demonstrate that, in addition to the well-known efficient synthesis of organic compounds in plasmas, the yields of saturated species, e.g., ethane, may be higher than predicted by theory and that LIP provide a convenient and clean way of simulating planetary lightning and impact plasmas in the laboratory.

Scattergood, T. W.↗

Chemistry of the outer planets

Various aspects were studied of past or present chemistry in the atmospheres of the outer planets and their satellites using lab simulations. Three areas were studied: (1) organic chemistry induced by kinetically hot hydrogen atoms in the region of Jupiter's atmosphere containing the ammonia cirrus clouds; (2) the conversion of NH3 into N2 by plasmas associated with entry of meteors and other objects into the atmosphere of early Titan; and (3) the synthesis of simple hydrocarbons and HCN by lightning in mixtures containing N2, CH4, and NH3 representing the atmospheres of Titan and the outer planets. The results showed that: (1) hot H2 atoms formed from the photodissociation of NH3 in Jupiter's atmosphere could account for some of the atmospheric chemistry in the ammonia cirrus cloud region; (2) the thermalization of hot H2 atoms in atmospheres predominated by molecular H is not as rapid as predicted by elastic collision theory; (3) the net quantum loss of NH3 in the presence of a 200 fold excess of H2 is 0.02, much higher than was expected from the amount of H2 present; (4) the conversion of NH3 into N2 in plasmas associated with infalling meteors is very efficient and rapid, and could account for most of the N2 present on Titan; (5) the yields of C2H2 and HCN from lightning induced chemistry in mixtures of CH4 and N2 is consistent with quenched thermodynamic models of the discharge core; and (6) photolysis induced by the UV light emitted by the gases in the hot plasmas may account for some, if not most, of the excess production of C2H6 and the more complex hydrocarbons.

Scattergood, Thomas W.↗

Generalized hypercube structures and hyperswitch communication network

This paper discusses an ongoing study that uses a recent development in communication control technology to implement hybrid hypercube structures. These architectures are similar to binary hypercubes, but they also provide added connectivity between the processors. This added connectivity increases communication reliability while decreasing the latency of interprocessor message passing. Because these factors directly determine the speed that can be obtained by multiprocessor systems, these architectures are attractive for applications such as remote exploration and experimentation, where high performance and ultrareliability are required. This paper describes and enumerates these architectures and discusses how they can be implemented with a modified version of the hyperswitch communication network (HCN). The HCN is analyzed because it has three attractive features that enable these architectures to be effective: speed, fault tolerance, and the ability to pass multiple messages simultaneously through the same hyperswitch controller.

Young, Steven D.↗

Non-LTE models of Titan's upper atmosphere

Models for the thermal structure of Titan's upper atmosphere, between 0.1 mbar and 0.01 nbar are presented. The calculations include non-LTE heating/cooling in the rotation-vibration bands of CH4, C2H2, and C2H6, absorption of solar IR radiation in the near-IR bands of CH4 and subsequent cascading to the nu-4 band of CH4, absorption of solar EUV and UV radiation, thermal conduction and cooling by HCN rotational lines. Unlike earlier models, the calculated exospheric temperature agrees well with observations, because of the importance of HCN cooling. The calculations predict a well-developed mesopause with a temperature of 135-140 K at an altitude of approximately 600 km and pressure of about 0.1 microbar. The mesopause is at a higher pressure than predicted by earlier calculations because non-LTE radiative transfer in the rotation-vibration bands of CH4, C2H2, and C2H6 is treated in an accurate manner. The accuracy of the LTE approximation for source functions and heating rates is discussed.

Yelle, Roger V.↗

CN radical reactions with hydrogen cyanide and cyanogen - Comparison of theory and experiment

The method of laser photolysis/laser-induced fluorescence is used to obtain absolute rate constants for CN radical reactions with HCN and C2N2. The rate constants were found to be temperature-dependent in the range 300-740 K and pressure independent in the range 100-600 Torr. Rice-Remsperger-Kassel-Marcus theory for both reactions employing the transition state parameters obtained by the BAC-MP4 method are made. These calculations yielded reasonable results for the CN + HCN reaction, predicting both the temperature dependence and pressure independence. No pressure effect was observed in the pressure range 100-1000 Torr at temperatures below 900 K, confirming the experimental results.

Yang, D. L.↗

A Reexamination of Amino Acids in Lunar Soils: Implications for the Survival of Exogenous Organic Material During Impact Delivery

Using a sensitive high performance liquid chromatography technique, we have analyzed both the hot water extract and the acid hydrolyzed hot water extract of lunar soil collected during the Apollo 17 mission. Both free amino acids and those derived from acid labile precursors are present at a level of roughly 15 ppb. Based on the D/L amino acid ratios, the free alanine and aspartic acid observed in the hot water extract can be entirely attributed to terrestrial biogenic contamination. However, in the acid labile fraction, precursors which yield amino acids are apparently present in the lunar soil. The amino acid distribution suggests that the precursor is probably solar wind implanted HCN. We have evaluated our results with regard to the meteoritic input of intact organic compounds to the moon based on an upper limit of less than or equal to 0.3 ppb for alpha-aminoisobutyric acid, a non-protein amino acid which does not generally occur in terrestrial organisms and which is not a major amino acid produced from HCN, but which is a predominant amino acid in many carbonaceous chondrites. We find that the survival of exogenous organic compounds during lunar impact is less than or equal to 0.8%. This result represents an example of minimum organic impact survivability. This is an important first step toward a better understanding of similar processes on Earth and on Mars, and their possible contribution to the budget of prebiotic organic compounds on the primitive Earth.

Brinton, Karen L. F.↗

Interstellar and cometary ices: Molecular emission from comet Hale-Bopp

Observations of rotational translations of neutral molecules, radicals and ions in the comet Hale-Bopp are reported on. Sample spectra and maps of the emission for the J = 1 to 0 transition of HCN, the J = 2 to 1 transition of CS and the J = 1 to 0 transition of HCO+ are presented. While the emission from HCN is typically centered on the position of the nucleus and is symmetric, the emission from HCO+ exhibits multiple peaks, together with evidence for acceleration away from the nucleus.

Irvine, W. M.↗

Atmos/Atlas 3 Infrared Profile Measurements of Trace Gases in The November 1994 Tropical and Subtropical Upper Troposphere

Vertical mixing ratio profiles of four relatively long-lives gases, HCN, C2H2, CO, and C2H6, have been retrieved from 0.01/cm resolution infrared solar occultation spectra recorded between latitudes of 5.3degN and 31.4degN. The observations were obtained by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer during the Atmospheric Laboratory for Applications and Science (ATLAS) 3 shuttle flight, 3-12 November 1994. Elevated mixing ratios below the tropopause were measured for these gases during several of the occultations. The positive correlations obtained between the simultaneously measured mixing ratios suggest that the enhancements are likely the result of surface emissions, most likely biomass burning and/or urban industrial activities, followed by common injection via deep convective transport of the gases to the upper troposphere. The elevated levels of HCN may account for at least part of the "missing NO," in the upper troposphere. Comparisons of the observations with values measured during a recent aircraft campaign are presented.

Rinsland, C. P.↗

The Properties and Effects of Titan's Organic Haze

Titan's organic haze is the the dominant absorber of solar energy in Titan's atmosphere, creating an anti-greenhouse effect. Its variation over time may have had important implications for Titan's surface temperature. The haze is potentially an important sink of photochemically produced carbon and nitrogen compounds. Laboratory simulations and microphysical models suggest that the haze is a sink for C of 4 x 10(exp 8)/ sq cm s, and a sink for N of 1 x 10(exp 8)sq cm s. The C sink is small compared to condensation of hydrocarbons but the sink for N is comparable to the total production rate of HCN. Because estimates of the eddy diffusion profile on Titan have been based on the HCN profile, inclusion of this additional sink for N will affect estimates for all transport processes in Titan's atmosphere.

McKay, Christopher P.↗

Prebiotic Nitrogen Fixation by FeS Reduction of Nitrite Under Acidic Conditions

Theories for the origin of life require the availability of reduced nitrogen for the formation of such species as amino acid and nucleic acids. In a strongly reducing atmosphere, compounds essential to the chemical evolution of life, such as amino acids, can form by reactions between HCN, NH3, and carbonyl compounds produced in spark discharges. However, under non-reducing atmospheres, electric discharges produced NO rather than HCN or NH3. This raises the questions of; how ammonia can be formed under a neutral atmosphere, and what conditions are needed such formation to occur? On possibility is the conversion of NO into nitric and nitrous acids (through HNO) and rained into the oceans. The reduction of nitrite by aqueous Fe(II) (6 Fe(+2) + 7 H(+) + NO2(-) yields 6 Fe(III) + 2 H2O + NH3) such as was present on the early Earth could then have produced ammonia. However, this reaction does not proceed at pHs less than 7.3. An alternative is reduction by other forms of Fe(II), such as FeS. We will present results that show that FeS can reduce nitrite to ammonia at pHs as low as pH 5 under a variety of conditions.

Summers, David P.↗

Theoretical Studies of the Extra-terrestrial Chemistry of Biogenic Elements and Compounds

Results are presented on the following:(A) Ab initio quantum chemical studies of reactions in astrophysical ices.Theoretical electronic structure calculations were used to investigate reactions between formaldehyde (H2CO) and both hydrogen cyanide (HCN) and isocyanide (HNC) in search of other favorable reactions such as ammonia-formaldehyde addition, which was found in a recent theoretical study to be strongly enhanced when it occurs within cold ices.The present study examines further reactions between this product and H2CO in ices.(B) Heterogeneous hydrogenation of CO and H2CO on icy grain mantles.Formaldehyde (H2CO) and methanol (CH30H) are thought to be produced in the interstellar medium by the successive hydrogenation of carbon monoxide (CO) on grain surfaces. In the gas phase, the steps in which H adds to CO and H2CO possess modest barriers and are too inefficient to account for the observed abundances. Recent laboratory work has confirmed that formaldehyde and methanol are formed when H atoms are deposited on CO ice at 12 K. The present study employed ab initio quantum chemical calculations to investigate the impact of water ice on the sequential hydrogenation of CO.(C) Ice-bound condensed-phase reactions involving formic acid (HCOOH), methylenimine (CH2NH), hydrogen cyanide (HCN), hydrogen isocyanide (HNC), and ammonia ( 3) were investigated in order to characterize possible pathways to larger organic species that are efficient at the cold temperatures prevalent in cometary nuclei and the interstellar medium. (D) Pathways to glycine and other amino acids in ultraviolet-irradiated ices determined via quantum chemical modeling.(E) Photoionization in ultraviolet processing of astrophysical ice analogs at cryogenic temperatures.

Woon, David E.↗