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At least 559 records · Page 31
All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

The Lifetimes of Nitriles (-C*N) and Acids (-COOH) during Ultraviolet Photolysis and Their Survival in Space

Nitriles are one of the most common classes of molecules observed in the gas phase in space, with over a dozen having been positively identified in interstellar and circumstellar environments through the detection of their rotational transitions. Acids, in contrast, are much less common. In this paper we present laboratory data comparing the stability of two structurally related acid-nitrile pairs to ultraviolet (UV) photolytic destruction: acetic acid vs. acetonitrile (CH3-COOH vs. CH3-CN) and glycine vs. aminoacetonitrile (H2N-CH2-COOH vs. H2N-CH2-CN). We find that the nitriles are destroyed ten and five times more slowly (respectively) by UV photolysis than are the corresponding acids. This suggests that whatever their relative formation rates, acids may be less abundant than nitriles in interstellar environments in part because they are more rapidly destroyed by photolysis. The results of this infrared (IR) spectral matrix isolation study indicate that during the lifetime of a typical interstellar cloud, even in its darkest regions, a population of acids in the gas phase will likely be diminished by at least half. Since aminoacetonitrile is a precursor to the amino acid glycine, and far more stable, presolar aminoacetonitrile may be a contributor to the deuterium enriched glycine detected in meteorites. It would clearly be informative to search for aminoacetonitrile (the nitrile corresponding to glycine) in the regions where the amino acid glycine has been reported.

Bernstein, Max P.↗
NASA NTRS2004

Observing Star and Planet Formation in the Submillimeter and Far Infrared

Stars from in the densest parts of cold interstellar clouds which-due to presence of obscuring dust-cannot be observed with optical telescopes. Recent rapid progress in understanding how stars and planets are formed has gone hand in hand with our ability to observe extremely young systems in the infrared and (submillimeter) spectral regimes. The detections and silhouetted imaging of disks around young objects in the visible and NIR have demonstrated the common occurrence of circumstellar disks and their associated jets and outflows in star forming regions. However, in order to obtain quantitative information pertaining to even earlier evolutionary phases, studies at longer wavelengths are necessary. From spectro-photometric imaging at all wavelengths we learn about the temperature and density structure of the young stellar environment. From narrow band imaging in the far infrared and submillimeter spectral regimes we can learn much about the velocity structure and the chemical makeup (pre-biotic material) of the planet-forming regions.

Yorke, Harold W.↗
NASA NTRS1997

First astronomical detection of the cumulene carbon chain molecule H2C6 in TMC-1

The cumulene carbenes are important components of hydrocarbon chemistry in low-mass star-forming cores. Here we report the first astronomical detection of the long-chain cumulene carbene H2C6 in the interstellar cloud TMC-1, from observations of two of its rotational transitions: J(K,K') = 7(1,7) --> 6(1,6) at 18.8 GHz and 8(1,8) --> 7(1,7) at 21.5 GHz, using NASA's Deep Space Network 70 m antenna at Goldstone, California. In addition we also observed the shorter cumulene carbene H2C4 at the same position. The fractional abundance of H2C6 relative to H2 is about 4.7 x 10(-11) and that of H2C4 is about 4.1 x 10(-9). The abundance of H2C6 is in fairly good agreement with gas-phase chemical models for young molecular cloud cores, but the abundance of H2C4 is significantly larger than predicted.

NASA Discipline Exobiology↗
NASA NTRS1997

The rate of the reaction between C2H and C2H2 at interstellar temperatures

The reaction between the radical C2H and the stable hydrocarbon C2H2 is one of the simplest neutral-neutral hydrocarbon reactions in chemical models of dense interstellar clouds and carbon-rich circumstellar shells. Although known to be rapid at temperatures > or = 300 K, the reaction has yet to be studied at lower temperatures. We present here ab initio calculations of the potential surface for this reaction and dynamical calculations to determine its rate at low temperature. Despite a small potential barrier in the exit channel, the calculated rate is large, showing that this reaction and, most probably, more complex analogs contribute to the formation of complex organic molecules in low-temperature sources.

Non-NASA Center↗
NASA NTRS1994

Fullerenes in an impact crater on the LDEF spacecraft

The fullerenes C60 and C70 have been found to occur naturally on Earth and have also been invoked to explain features in the absorption spectra of interstellar clouds. But no definitive spectroscopic evidence exists for fullerenes in space and attempts to find fullerenes in carbonaceous chondrites have been unsuccessful. Here we report the observation of fullerenes associated with carbonaceous impact residue in a crater on the Long Duration Exposure Facility (LDEF) spacecraft. Laser ionization mass spectrometry and Raman spectroscopy indicate the presence of fullerenes in the crater and in adjacent ejecta. Man-made fullerenes survive experimental hypervelocity (approximately 6.1 km s-1) impacts into aluminium targets, suggesting that space fullerenes contained in a carbonaceous micrometeorite could have survived the LDEF impact at velocities towards the lower end of the natural particle encounter range (<13 km s-1). We also demonstrate that the fullerenes were unlikely to have formed as instrumental artefacts, nor are they present as contaminants. Although we cannot specify the origin of the fullerenes with certainty, the most plausible source is the chondritic impactor. If, alternatively, the impact produced the fullerenes in situ on LDEF, then this suggests a viable mechanism for fullerene production in space.

long duration↗
NASA NTRS1991

Ab initio study of C + H3+ reactions

The reaction C + H3+ --> CH(+) + H2 is frequently used in models of dense interstellar cloud chemistry with the assumption that it is fast, i.e. there are no potential energy barriers inhibiting it. Ab initio molecular orbital study of the triplet CH3+ potential energy surface (triplet because the reactant carbon atom is a ground state triplet) supports this hypothesis. The reaction product is 3 pi CH+; the reaction is to exothermic even though the product is not in its electronic ground state. No path has been found on the potential energy surface for C + H3+ --> CH2(+) + H reaction.

NASA Discipline Exobiology↗
NASA NTRS1998

Near-infrared spectroscopy of the proto-planetary nebula CRL 618 and the origin of the hydrocarbon dust component in the interstellar medium

A new 2.8-3.8 micrometers spectrum of the carbon-rich protoplanetary nebula CRL 618 confirms the previous detection of a circumstellar 3.4 micrometers absorption feature in this object (Lequeux & Jourdain de Muizon). The high resolution and high signal-to-noise ratio of our spectrum allow us to derive the detailed profile of this absorption feature, which is very similar to that observed in the spectrum of the Galactic center and also resembles the strong 3.4 micrometers emission feature in some post-asymptotic giant branch stars. A weak 3.3 micrometers unidentified infrared band, marginally detected in the CRL 618 spectrum of Lequeux & Jourdain de Muizon, is present in our spectrum. The existence of the 3.4 micrometers feature implies the presence of relatively short-chained, aliphatic hydrocarbon materials (-CH2-/-CH3 approximately = 2-2.5) in the circumstellar environment around CRL 618. It also implies that the carriers of the interstellar 3.4 micrometers feature are produced at least in part in circumstellar material, and it calls into question whether any are produced by the processing of interstellar ices in dense interstellar clouds, as has been previously proposed. Other features in the spectrum are recombination lines of hydrogen, rotational and vibration-rotation lines of molecular hydrogen, and a broad absorption probably due to a blend of HCN and C2H2 bands.

Spectroscopy, Near-Infrared↗
NASA NTRS1987

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↗
NASA NTRS1998

Deuterium in comet C/1995 O1 (Hale-Bopp): detection of DCN

Deuterated hydrogen cyanide (DCN) was detected in a comet, C/1995 O1 (Hale-Bopp), with the use of the James Clerk Maxwell Telescope on Mauna Kea, Hawaii. The inferred deuterium/hydrogen (D/H) ratio in hydrogen cyanide (HCN) is (D/H)HCN = (2.3 +/- 0.4) x 10(-3). This ratio is higher than the D/H ratio found in cometary water and supports the interstellar origin of cometary ices. The observed values of D/H in water and HCN imply a kinetic temperature >/=30 +/- 10 K in the fragment of interstellar cloud that formed the solar system.

Non-NASA Center↗
NASA NTRS2003

Facile Generation and Storage of Polycyclic Aromatic Hydrocarbon Ions in Astrophysical Ices

In situ ultraviolet-visible absorption and emission studies of vacuum ultraviolet (VUV) irradiated water-rich, cosmic ice analogs containing polycyclic aromatic hydrocarbons (PAHs) are described. W V irradiation of 12 K water ices containing the PAHs naphthalene (H2O/C10H8 = 200) and 4-methylpyrene (H2O/C17H12 > 500) readily converts the PAHs into their cation form (PAH(+)). Under these conditions, PAH photoionization is the predominant reaction. These ions are trapped and stored in the ices at temperatures between 10 and 50 K, a temperature domain common to ices throughout interstellar clouds and the solar system. Unlike the approx.15% ionization typical after W V irradiation of PAHs isolated in rare-gas matrices, in water ice, PAH photoionization and storage proceed efficiently and almost quantitatively with a greater than 70% ionization yield. As the temperature is increased from 50 to 150 K, the PAH ion bands slowly diminish as the PAH ions ultimately react to form more complex organic species involving the water host. The chemical, spectroscopic, and physical properties of these ion-rich ices can be important in icy objects such as molecular clouds, comets, and planets. Several astrophysical applications are presented.

Gudipati, Murthy S.↗
NASA NTRS1993

Cirrus and Future Space Based Astronomy

Astronomical observations from space make possible observations of sensitivity and spatial resolution impossible in the past. This increase in sensitivity will both make possible the observation of new phenomena and will bring observations against limitations not encountered before. This paper discusses the effects that infrared cirrus and diffuse interstellar clouds will have on space based observations. Some special opportunities provided by space observations of cirrus are presented and a partial list of currently planned observations of cirrus by space telescopes is given.

cirrus observations sensitivity stellar clouds spa↗
NASA NTRS2006

Lifetimes and Oscillator Strengths for Ultraviolet Transitions in P II, Cl II and Cl III

Oscillator strengths for transitions in P II, Cl II and Cl III are derived from lifetimes and branching factions measured with beam-foil techniques. The focus is on the multiplets with a prominent interstellar line at 1153 A in P II which is seen in spectra of hot stars, and the lines at 1071 A in Cl II and 1011 A in Cl III whose lines are seen in spectra of diffuse interstellar clouds and the Io torus acquired with the Far Ultraviolet Spectroscopic Explorer. These data represent the first complete set of experimental f-values for the lines in the multiplets. Our results for P II (lambda)1153 agree well with Curtis semi-empirical predictions, as well as the large scale computations by Hibbert and by Tayal. The data for Cl II (lambda)1071 also agree very well with the most recent theoretical effort and with Morton s newest recommendations. For Cl III, however, our f-values are significantly larger than those given by Morton; instead, they are more consistent with recent large-scale theoretical calculations. Extensive tests provide confirmation that LS coupling rules apply to the transitions for the multiplets in Cl II and Cl III.

Cheng, S.↗
NASA NTRS2006

Vibrational and rotational quenching of CO by collisions with H, He, and H2

Collisional quenching of molecular species is an important process in a variety of astrophysical environments including interstellar clouds, photodissociation regions, and cool stellar/planetary atmospheres. In this work, quantum mechanical scattering calculations are presented for the rotational and vibrational relaxation of rotationally-excited CO due to collisions with H, He and H2 for collision energies between 10(exp -6) and approx.15000/cm. The calculations were performed using the close-coupling approach and the l-labeled form of the coupled-states approximation. Cross sections and rate coefficients for the quenching of the v=0-2, j=0-6 levels of CO are presented and comparisons with previous calculations and measurements, where available, are provided.

Yang, Benhui↗
NASA NTRS2006

Oscillator Strengths and Predissociation Widths for Rydberg Transitions in Carbon Monoxide

CO is used as a probe of astronomical environments ranging from planetary atmospheres and comets to interstellar clouds and the envelopes surrounding stars near the end of their lives. One of the processes controlling the CO abundance and the ratio of its isotopomers is photodissociation. Accurate oscillator strengths for Rydberg transitions are needed for modeling this process. Absorption bands were analyzed by synthesizing the profiles with codes developed independently in Meudon and Toledo. Each synthetic spectrum was adjusted to match the experimental one in a non-linear least-squares fitting procedure with the band oscillator strength, the line width (instrumental and predissociation.

Federman, Steven R.↗
NASA NTRS2007

Quantum Chemical Evaluation of the Astrochemical Significance of Reactions between S Atom and Acetylene or Ethylene

Addition-elimination reactions of S atom in its P-3 ground state with acetylene (C2H2) and ethylene (C2H4) were characterized with both molecular orbital and density functional theory calculations employing correlation consistent basis sets in order to assess the likelihood either reaction might play a general role in astrochemistry or a specific role in the formation of S2 (X (sup 3 SIGMA (sub g) (sup -)) via a mechanism proposed by Saxena and Misra (Mon. Not. R. Astron. Soc. 1995, 272, 89). The acetylene and ethylene reactions proceed through C2H2S ((sup 3)A")) and C2H4S ((sup 3)A")) intermediates, respectively, to yield HCCS ((sup 2)II)) and C2H3S ((sup 2)A')). Substantial barriers were found in the exit channels for every combination of method and basis set considered in this work, which effectively precludes hydrogen elimination pathways for both S + C2H2 and S + C2H4 in the ultracold interstellar medium where only very modest barriers can be surmounted and processes without barriers tend to predominate. However, if one or both intermediates is formed and stabilized efficiently under cometary or dense interstellar cloud conditions, they could serve as temporary reservoirs for S atom and participate in reactions such as S + C2H2S (right arrow) S2 = C2H2 or S + C2H4S (right arrow) S2 + C2H4. For formation and stabilization to be efficient, the reaction must possess a barrier height small enough to be surmountable at low temperatures yet large enough to prevent redissociation to reactants. Barrier heights computed with B3LYP and large basis sets are very low, but more rigorous QCISD(T) and RCCSD(T) results indicate that the barrier heights are closer to 3-4 kcal/mol. The calculations therefore indicate that S + C2H2 or S + C2H4 could contribute to the formation of S2 in comets and may serve as a means to gauge coma temperature. The energetics of the ethylene reaction are more favorable.

Woon, David E.↗
NASA NTRS2011

Microwave Spectroscopy of Complex Molecules Around the Young Protostar Chamaeleon MMS1

Observations are presented of emission lines from organic molecules at frequencies 30-100 GHz in the vicinity of the extremely young, chemically rich, very low-luminosity protostar and candidate first hydrostatic core Chamaeleon MMS1. Column densities are derived and emission maps are presented for species including polyynes, cyanopolyynes, sulphuretted carbon-chains and methanol. Emission from the carbon-chain-bearing species peaks very near to the protostar; methanol peaks about 0.1 pc further away. The mean molecular hydrogen number density is calculated to be 10(exp 6) per cc. and the gas kinetic temperature is in the range 4-7 K. The abundances of long carbon chains (including C6H and HC7N) are very large -- similar to those found in the most carbon-chain-rich regions of the Galaxy, and indicative of a non-equilibrium carbon chemistry. The observed methanol and acetaldehyde abundances indicate active grain-surface chemistry and desorption processes. The carbon-chain anions C4H- and C6H- were not detected and the upper limit on the anion-to-neutral ratio for C4H- is less than 0.02% and for C6H-, less than 10%. These values are consistent with previous observations in interstellar clouds and low-mass protostars. Deuterated HC3N and c-C3H2 were detected, with fractionation ratios of about 4%, and 22%, respectively. A low c-C3H2 ortho-to-para ratio was measured, which is consistent with a molecular hydrogen ortho-to-para ratio of close to zero and implies a relatively young chemical age (less than about 10(exp 5) yr) for the matter surrounding Cha-MMS1. These observations show that a high level of chemical complexity can be present in star-forming gas.

Cordiner, Martin A.↗
NASA NTRS2011

Anions in Cometary Comae

The presence of negative ions (anions) in cometary comae is known from Giotto mass spectrometry of IP/Halley. The anions 0-, OH-, C-, CH- and CN- have been detected, as well as unidentified anions with masses 22-65 and 85-110 amu (Chaizy et al. 1991). Organic molecular anions are known to have a significant impact on the charge balance of interstellar clouds and circumstellar envelopes and have been shown to act as catalysts for the gas-phase synthesis of larger hydrocarbon molecules in the ISM, but their importance in cometary comae has not yet been explored. We present details of the first attempt to model the chemistry of anions in cometary comae. Based on the combined chemical and hydro dynamical model of Rodgers & Charnley (2002), we investigate the role of large carbon-chain anions in cometary coma chemistry. We calculate the effects of these anions on coma thermodynamics, charge balance and examine their impact on molecule formation.

Charnley, Steven B.↗
NASA NTRS2011

A Theoretical Investigation of the Plausibility of Reactions Between Ammonia and Carbonyl Species (Formaldehyde, Acetaldehyde, and Acetone) in Interstellar Ice Analogs at Ultracold Temperatures

We have reexamined the reaction between formaldehyde and ammonia, which was previously studied by us and other workers in modestly sized cluster calculations. Larger model systems with up to 12H2O were employed, and reactions of two more carbonyl species, acetaldehyde and acetone, were also carried out. Calculations were performed at the B3LYP/6-31+G** level with bulk solvent effects treated with a polarizable continuum model; limited MP2/6-31+G** calculations were also performed. We found that while the barrier for the concerted proton relay mechanism described in previous work remains modest, it is still prohibitively high for the reaction to occur under the ultracold conditions that prevail in dense interstellar clouds. However, a new pathway emerged in more realistic clusters that involves at least one barrierless step for two of the carbonyl species considered here: ammonia reacts with formaldehyde and acetaldehyde to form a partial charge transfer species in small clusters (4H2O) and a protonated hydroxyamino intermediate species in large clusters (9H2O, 12H2O); modest barriers that decrease sharply with cluster size are found for the analogous processes for the acetone-NH3 reaction. Furthermore, if a second ammonia replaces one of the water molecules in calculations in the 9H2O clusters, deprotonation can occur to yield the same neutral hydroxyamino species that is formed via the original concerted proton relay mechanism. In at least one position, deprotonation is barrierless when zero-point energy is included. In addition to describing the structures and energetics of the reactions between formaldehyde, acetaldehyde, and acetone with ammonia, we report spectroscopic predictions of the observable vibrational features that are expected to be present in ice mixtures of different composition.

Chen, Lina↗