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At least 271 records · Page 15

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NASA NTRS1993

Oxidation state of the Earth's upper mantle during the last 3800 million years: Implications for the origin of life

A popular, as well as scientifically rigorous, scenario for the origin of life on Earth involves the production of organic molecules by interaction of lightning (or other forms of energy) with a chemically reducing atmosphere in the early history of Earth. Experiments since the 1950's have convincingly demonstrated that the yield of organic molecules is high when the atmosphere contains molecular hydrogen, methane, ammonia, and water vapor. Additional work has also shown that such a highly reducing atmosphere might not, however, have been sufficiently long-lived in the presence of intense solar ultraviolet radiation for life to have formed from it. One way of maintaining such an atmosphere would be to have a continual replenishment of the reduced gases by prolonged volcanic outgassing from a reducing of Earth's interior. The length of time that this replenishment might need to continue is in part constrained by the flux of asteroids onto the Earth's surface containing sufficient energy to destroy most, if not all, life that had developed up to that point in time. If a reducing atmosphere is a key ingredient for the origin of life on Earth, the time of the last environmental sterilization due to large impacts would be an important constraint. In a deep marine setting (e.g., hydrothermal vent), the last global sterilization might have occurred at 4200-4000 Ma. On the Earth's surface, the last global sterilization event might have occurred at 4000-3700 Ma. If these are meaningful constraints, how likely is it that a reducing atmosphere could have survived on the Earth until about 3800 Ma ago? Due to the importance of replenishing this atmosphere with reducing components by volcanic outgassing from the mantle, geochemical information on the history of the mantle's oxidation state would be useful for addressing this question. Geochemical and experimental data discussed in this abstract suggest that extrusive mafic volcanics derived from the upper mantle have had oxidation states near the fayalite-magnetite quartz buffer throughout the last 3800 Ma. At magmatic temperatures, the gases released from volcanoes having this oxidation state would have been, as they are today, composed dominantly of carbon dioxide and water vapor, and would not contain the ingredients for maintaining a reducing atmosphere. Consequently, geochemical data do not favor the survival of a reducing atmosphere until about 3800 Ma. Alternative venues and pathways for the origin of life need to be investigated (e.g., hydrothermal vents along oceanic ridges).

Delano, J. W.↗

NASA NTRS1999

Carbon chain abundance in the diffuse interstellar medium

Thanks to the mid-IR sensitivities of the ISO and IRTS orbiting spectrometers it is now possible to search the diffuse interstellar medium for heretofore inaccessible molecular emission. In view of the recent strong case for the presence of C(7-) (Kirkwood et al. 1998, Tulej et al. 1998),and the fact that carbon chains possess prominent infrared active modes in a very clean portion of the interstellar spectrum, we have analyzed the IRTS spectrum of the diffuse interstellar medium for the infrared signatures of these species. Theoretical and experimental infrared band frequencies and absolute intensities of many different carbon chain species are presented. These include cyanopolyynes, neutral and anionic linear carbon molecules, and neutral and ionized, even-numbered, hydrogenated carbon chains. We show that--as a family--these species have abundances in the diffuse ISM on the order of 10(-10) with respect to hydrogen, values consistent with their abundances in dense molecular clouds. Assuming an average length of 10 C atoms per C-chain implies that roughly a millionth of the cosmically available carbon is in the form of carbon chains and that carbon chains can account for a few percent of the visible to near-IR diffuse interstellar band (DIB) total equivalent width (not DIB number).

Carbon/analysis/chemistry↗

NASA NTRS2014

1-Azaniumylcyclobutane-1-carboxylate monohydrate

In the title compound, C5H9NO2H2O, the amino acid is in the usual zwitterionic form involving the carboxylate group. The cyclobutane backbone of the amino acid is disordered over two conformations, with occupancies of 0.882 (7) and0.118 (7). In the crystal, NH O and OH O hydrogen bonds link the zwitterions [with the water molecule involved as both acceptor (with the NH3+) and donor (through a single carboxylate O from two different aminocyclobutane carboxylatemoities)], resulting in a two-dimensional layered structure lying parallel to (100).

Azaniumylcyclobutane↗

NASA NTRS1976

Infrared spectra of molecules and materials of astrophysical interest

The vibrational spectra from 4,000 to 33/cm of several molecules which may be present in the atmosphere of the Jovian planets or exist in outer space were studied. These studies have been made to provide vibrational frequencies which can be used to: (1) determine the composition of the cloud covers of several of the planets, (2) provide structural information under favorable circumstances, (3) provide necessary data from which accurate thermodynamic data can be calculated, and (4) furnish information as to the nature of the potential energy function of the molecules and forces acting within them. Some of the molecules studied can be produced photochemically from methane, ammonia, and hydrogen sulfide which are thought to be constituents of the planets with reducing atmospheres. Some of the compounds will polymerize under ultraviolet radiation and drop out of the atmospheres. However, planets with a hot base, like that of Jupiter, may rebuild molecules destroyed photochemically. These criteria were used in selecting the compounds under study.

Durig, J. R.↗

NASA NTRS1971

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.↗

NASA NTRS1976

H2 molecules and the intercloud medium

The paper discusses expected column densities of H2 in the intercloud medium and the possible use of molecules as indicators of intercloud physical conditions. Molecule formation by the H(-) process and on graphite grains is treated, and it is shown that the Barlow-Silk hypothesis of a 1-eV semichemical hydrogen-graphite bond leads to a large enhancement of the intercloud molecule-formation rate. Rotational-excitation calculations are presented for both cloud and intercloud conditions which show, in agreement with Jura (1975), that the presently observed optically thin H2 absorption components are more likely to originate in cold clouds than in the intercloud medium.

Hill, J. K.↗

NASA NTRS2012

Searching for Bio-Precursors and Complex Organic Molecules in Space using the GBT

Using the latest microwave receiver technology, large organic molecules with abundances as low as approx. 10(exp -11) times that of molecular hydrogen are detectable in cold interstellar clouds via their rotational emission line spectra. We report new observations to search for complex molecules, including molecules of possible pre-biotic importance, using the newly-commissioned Kband focal plane array (KFPA) of the NRAO Robert C. Byrd Green Bank Telescope. Spectra are presented of the dense molecular cloud TMC-1, showing strict upper limits on the level of emission from nitrogen-bearing rings pyrimidine, quinoline and iso-quinoline, carbon-chain oxides C60, C70, HC60 and HC70, and the carbon-chain anion C4H-. The typical RMS brightness temperature noise levels we achieved are approx. 1 mK at around 20 GHz.

Cordiner, M.↗

NASA NTRS2017

Limits to Creation of Oxygen-Rich Atmospheres on Planets in the Outer Reaches of the Conventional Habitable Zone

Abundant free oxygen appears to be a requirement for macroflora and macrofauna. To the best of our knowledge, a general discussion of which habitable planets are conducive to oxygen has not taken place. Theories for the rise of oxygen fall into 4 categories: (i) It is governed by an intrinsic rate of biological innovation, independent of environmental factors. (ii) It is caused by mantle evolution, probably consequent to secular cooling. (iii) It is caused by hydrogen escape, which irreversibly oxidizes the Earth. (iv) It is Gaia's response to the brightening Sun, its rise prevented until reduced greenhouse gases were no longer needed to maintain a clement climate. All but the first of these make implicit astronomical predictions that can be quantified and made explicit. Here we address the third hypothesis. In this hypothesis hydrogen escape acts like an hourglass that continues until all relevant reduced mineral buffers have been oxidized (titrated, as it were) and the surface made safe for O2. The hypothesis predicts that abundant free O2 will be absent from habitable planets that have not experienced significant hydrogen escape. Where hydrogen escape is modest or insignificant, the atmosphere can be approximated as hydrostatic, which makes assessing radiative cooling by embedded molecules, atoms, and ions such as CO2 and H3+ straightforward. In particular, H2 is efficient at exciting non-LTE CO2 15 micron emission, which makes radiative cooling very effective when H2 is abundant. We can therefore map out the region of phase space in which habitable planets do not lose hydrogen, and therefore do not develop O2 atmospheres. A related matter is the power of radiative cooling by embedded molecules to enforce the diffusion limit to hydrogen escape. This matter in particular is relevant to addressing the empirical observation that rocky planets with thin or negligible atmospheres are rarely or never bigger than approx.1.6 Earth radii.

Zahnle, Kevin↗

NASA NTRS1979

Molecule formation and infrared emission in fast interstellar shocks. I Physical processes

The paper analyzes the structure of fast shocks incident upon interstellar gas of ambient density from 10 to the 7th per cu cm, while focusing on the problems of formation and destruction of molecules and infrared emission in the cooling, neutral post shock gas. It is noted that such fast shocks initially dissociate almost all preexisting molecules. Discussion covers the physical processes which determine the post shock structure between 10 to the 4 and 10 to the 2 K. It is shown that the chemistry of important molecular coolants H2, CO, OH, and H2O, as well as HD and CH, is reduced to a relatively small set of gas phase and grain surface reactions. Also, the chemistry follows the slow conversion of atomic hydrogen into H2, which primarily occurs on grain surfaces. The dependence of this H2 formation rate on grain and gas temperatures is examined and the survival of grains behind fast shocks is discussed. Post shock heating and cooling rates are calculated and an appropriate, analytic, universal cooling function is developed for molecules other than hydrogen which includes opacities from both the dust and the lines.

Hollenbach, D.↗

NASA NTRS2016

Titan as the Abode of Life

Titan is the only world we know other than Earth that has a liquid on its surface. It has a thick atmosphere composed of nitrogen and methane with a thick organic haze. There are lakes, rain, and clouds of methane and ethane. Here, we address the question of carbon-based life living in Titan liquids. Photochemically produced organics, particularly acetylene, in Titan's atmosphere could be a source of biological energy when reacted with atmospheric hydrogen. Light levels on the surface of Titan are more than adequate for photosynthesis but the biochemical limitations due to the few elements available in the environment may lead only to simple ecosystems that only consume atmospheric nutrients. Life on Titan may make use of the trace metals and other inorganic elements produced by meteorites as they ablate in the atmosphere. It is conceivable that H2O molecules on Titan could be used in a biochemistry that is rooted in hydrogen bonds in a way that metals are used in enzymes by life on Earth. Previous theoretical work has shown possible membrane structures in Titan liquids, azotosomes, composed of small organic nitrogen compounds, such as acrylonitrile. The search for a plausible information molecule for life in Titan liquids remains an open research topic - polyethers have been considered and shown to be insoluble at Titan temperatures. Possible search strategies for life on Titan include looking for unusual concentrations of certain molecules reflecting biological selection. Homochirality is a special and powerful example of such biology selection. Environmentally, a depletion of hydrogen in the lower atmosphere may be a sign of metabolism. A discovery of life in liquid methane and ethane would be our first compelling indication that the Universe is full of diverse and wondrous life forms.

H2O molecules on Titan↗

NASA NTRS1972

The Lyman-alpha image of comet Tago-Sato-Kosaka /1969g/.

An f/2 objective-grating spectrograph aboard an Aerobee rocket recorded a faint image of Comet Tago-Sato-Kosaka (1969g) in L-alpha emission. Some sharpening of the image and reduction of film grain noise was accomplished by multiplying the picture's Fourier transform by an optimum filter function. After this processing, which was carried out digitally, the L-alpha comet image appeared as a nearly circularly symmetric diffuse glow approximately 800,000 km in diameter. There was also the suggestion of a faintly visible core of emission whose dimensions are less than 100,000 km. The sublimation of ice in the nucleus of the comet and the subsequent dissociation of the free water molecules by sunlight could produce a large cloud of hydrogen atoms around the comet. Resonant reradiation of solar L-alpha emission by this cloud is probably responsible for the most of the observed emission.

Jenkins, E. B.↗

NASA NTRS1974

Jupiter's ionosphere - Prospects for Pioneer 10

Model Jovian ionospheres are constructed for comparison with Pioneer 10 results. Electron density maxima are predicted at a level approximately 220 kilometers above an assumed reference height where the hydrogen density is 10 to the 16-th power molecules per cubic centimeter. It may be possible to use observations of the electron density to locate the turbopause. Attention is drawn to a possible strong source of ionized sodium from Io which might lead to large electron densities at low altitudes.

Atreya, S. K.↗

NASA NTRS1974

Measurements of ion-molecule reactions of He/+/, H/+/, and HeH/+/ with H2 and D2

Drift tube-mass spectrometer measurements of several ion-molecule reactions believed to be prominent in the hydrogen-helium upper atmosphere of Jupiter are described. The total rate constant at 300 K of the reaction of He(+) with H2 is about 1.1 x 10 to the neg 13 cu cm/sec. The reaction proceeds mainly by dissociative charge transfer to produce H(+), with a small portion going by charge transfer to H2(+) and by atom rearrangement to HeH(+). The rate coefficient increases slowly with ion mean energy to a value of 2.8 x 10 to the neg 13 at 0.18 eV. The rate of the corresponding reaction with deuterium, He(+) + D2, has the rate coefficient of about 5 x 10 to the neg 14 at 300 K. Measurements of the three-body reaction of H' and the two-body reaction of HeH' with H2 to form H3(+) ions are described.

Johnsen, R.↗

NASA NTRS1975

Ultraviolet studies of the interstellar gas

Sounding-rocket and satellite UV observations of interstellar gas clouds are reviewed with major attention given to Copernicus observations of interstellar absorption lines. Analysis of typical absorption-line data is outlined, and observations are reviewed for atomic hydrogen as well as interstellar H2, HD, and CO molecules. Investigations of atomic abundances in H I regions are summarized, measurements of atomic deuterium abundances in the interstellar gas are examined, and the properties of ionized interstellar gas are described. Theoretical analyses of the physical state of the interstellar gas are summarized with respect to ionization by energetic radiation, cool H I clouds, and the intercloud medium. The data obtained thus far are shown to indicate mean temperatures of about 80 K, particle densities between 10 and 1000 per cu cm, and a depletion of heavy elements that becomes greatly enhanced with increasing condensation temperature for those H I regions with strong H2 lines.

Spitzer, L., Jr.↗

NASA NTRS1976

Rotational excitation of CO by collisions with He, H, and H2 under conditions in interstellar clouds

Cross sections for rotational excitation of small molecules by low-energy collisions with helium and hydrogen can currently be obtained via accurate numerical solution of the quantum equations that describe both intermolecular forces and collision dynamics. The relevant methods are discussed in some detail and applied to compute excitation rates for carbon monoxide. These calculations also predict collision-induced spectral pressure-broadening constants which are in excellent agreement with available experimental data.

Green, S.↗

NASA NTRS1982

Chemisorption and reactions on clusters of nickel atoms

The nucleation and growth of metallic clusters on a substantially amorphous substrate are discussed with emphasis on the geometrical and electronic structure of the clusters. Several clusters of different symmetry containing five to nine nickel atoms were studied. It was found that the energy range of primary d-like states is not significantly different from the width of the d-band states in nickel metal, as long as the interatomic distance is comparable to that in the bulk metal. The approach of one or more molecules to the cluster is examined using at the hydrogenation of acetylene and the dehydrogenation of ethylene as examples.

Waber, J. T.↗

NASA NTRS1984

The ultraviolet astronomy mission: Columbus

An ultraviolet astronomy mission (Columbus) is described. It exploits the spectral region between 900 and 1200A, which is extremely rich in containing the Lyman lines of hydrogen and deuterium and the Lyman band of their molecules, together with the resonance lines of many important ions. High resolving power and high sensitivity provide a unique capability for studying the brightest members of neighboring galaxies, the HeI and HeII absorption systems in quasars out to a red shift of 2, and the halos of intervening galaxies. Complementary focal plane instruments are planned in order to allow observations to longer (2000A) and shorter (100A) wavelengths. This wide coverage embraces the resonance lines of all the cosmically abundant elements and a wide range of temperature zones up to 100 million K.

Wilson, R.↗

NASA NTRS1984

Variational calculations of muonic-molecule energy levels

The best variational energies obtained to date of the bound states of muonic molecules containing nucleons of unit charge or isotopes of hydrogen are reported. Hylleraas wave functions are used to describe the three-particle systems, and the convergence of the energies is carefully studied; as many as 440 terms have been included in some cases. These results are compared with the best previous values.

Bhatia, A. K.↗