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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

On the Formation of the C{sub 2}H{sub 6}O Isomers Ethanol (C{sub 2}H{sub 5}OH) and Dimethyl Ether (CH{sub 3}OCH{sub 3}) in Star-forming Regions

The structural isomers ethanol (CH{sub 3}CH{sub 2}OH) and dimethyl ether (CH{sub 3}OCH{sub 3}) were detected in several low-, intermediate-, and high-mass star-forming regions, including Sgr B2, Orion, and W33A, with the relative abundance ratios of ethanol/dimethyl ether varying from about 0.03 to 3.4. Until now, no experimental data regarding the formation mechanisms and branching ratios of these two species in laboratory simulation experiments could be provided. Here, we exploit tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS) to detect and analyze the production of complex organic molecules (COMs) resulting from the exposure of water/methane (H{sub 2}O/CH{sub 4}) ices to energetic electrons. The main goal is to understand the formation mechanisms in star-forming regions of two C{sub 2}H{sub 6}O isomers: ethanol (CH{sub 3}CH{sub 2}OH) and dimethyl ether (CH{sub 3}OCH{sub 3}). The results show that the experimental branching ratios favor the synthesis of ethanol versus dimethyl ether (31 ± 11:1). This finding diverges from the abundances observed toward most star-forming regions, suggesting that production routes on interstellar grains to form dimethyl ether might be missing; alternatively, ethanol can be overproduced in the present simulation experiments, such as via radical–radical recombination pathways involving ethyl and hydroxyl radicals. Finally, the PI-ReTOF-MS data suggest the formation of methylacetylene (C{sub 3}H{sub 4}), ketene (CH{sub 2}CO), propene (C{sub 3}H{sub 6}), vinyl alcohol (CH{sub 2}CHOH), acetaldehyde (CH{sub 3}CHO), and methyl hydroperoxide (CH{sub 3}OOH), in addition to ethane (C{sub 2}H{sub 6}), methanol (CH{sub 3}OH), and CO{sub 2} detected from infrared spectroscopy. The yield of all the confirmed species is also determined.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2012

FORMALDEHYDE AND METHANOL DEUTERATION IN PROTOSTARS: FOSSILS FROM A PAST FAST HIGH-DENSITY PRE-COLLAPSE PHASE

Extremely high deuteration of several molecules has been observed around low-mass protostars for a decade. Among them, formaldehyde and methanol present particularly high deuteration, with observations of abundant doubly and triply deuterated forms. Both species are thought to be mainly formed on interstellar grains during the low-temperature and dense pre-collapse phase by H and D atom additions on the iced CO. We present here a theoretical study of the formaldehyde and methanol deuteration obtained with our gas-grain model, GRAINOBLE. This model takes into account the multilayer nature of the mantle and explores the robustness of the results against the uncertainties of poorly constrained chemical and surface model parameters. The comparison of the model predictions with the observations leads to two major results: (1) the observed high deuteration is obtained during the last phase of the pre-collapse stage, when the density reaches {approx}5 Multiplication-Sign 10{sup 6} cm{sup -3}, and this phase is fast, lasting only several thousands years; and (2) D and H abstraction and substitution reactions are crucial in making up the observed deuteration ratios. This work shows the power of chemical composition as a tool to reconstruct the past history of protostars.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1990

Survival of carbon grains in shocks

Supernova shocks play a significant part in the life of an interstellar grain. In a typical 10 to the 9th power year lifetime, a grain will be hit by an average of 10 shocks of 100 km s(sup -1) or greater velocity, and even more shocks of lower velocity. Evaluation of the results of this frequent shock processing is complicated by a number of uncertainties, but seems to give about 10 percent destruction of silicate grains and about half that for graphite grains. Because of the frequency of shocking, the mineralogy and sizes of the grain population is predominately determined by shock processing effects, and not by the initial grain nucleation and growth environment. One consequence of the significant role played by interstellar shocks is that a certain fraction (up to 5 percent) of the carbon should be transformed into the diamond phase. Diamond transformation is observed in the laboratory at threshold shock pressures easily obtainable in grain-grain collisions in supernova shocks. Yields for transforming graphite, amorphous carbon, glassy carbon, and other nearly pure carbon solids into diamond are quite high. Impurities up to at least the 10 percent level (for oxygen) are tolerated in the process. The typical size diamond expected from shock transformation agrees well with the observed sizes in the Lewis et al. findings in meteoritic material. Isotropic anomalies already contained in the grain are likely to be retained through the conversion process, while others may be implanted by the shock if the grain is close to the supernova. The meteoritic diamonds are likely to be the results of transformation of carbon grains in grain-grain collisions in supernova shock waves.

Seab, C. Gregory↗
DOE OSTI2014

Reaction of the C{sub 3}(X{sup 1}Σ{sub g}{sup +}) carbon cluster with H{sub 2}S(X{sup 1}A{sub 1}), hydrogen sulfide: Photon-induced formation of C{sub 3}S, tricarbon sulfur

In this paper we report on the neutral-neutral reaction of the C{sub 3} carbon cluster with H{sub 2}S in solid inert argon at 12 K, conditions that mimic, in part, the surfaces of interstellar grains. In the first step of the reaction, a C{sub 3}•H{sub 2}S complex is formed via an almost barrierless entrance addition mechanism. This complex, stabilized by an estimated 7.45 kJ/mol (CCSD(T)/aug-cc-pVTZ//B3LYP/6-311++G(d,p) level), is formed by the interaction of a terminal carbon of C{sub 3} with a hydrogen in H{sub 2}S. This con-covalent complex displays a band at 2044.1 cm{sup −1} observed via Fourier transform infrared absorption spectroscopy. With the help of the MP2/aug-ccpVDZ level method, this band is assigned to the CC asymmetric vibration mode. When the complex is exposed to UV-visible photons (hν < 5.5 eV) the tricarbon sulfur C{sub 3}S molecule is identified, based on the appearance of a characteristic CC stretching band at 2047.5 cm{sup −1}. Calculated ground-state potential energy surfaces also confirm the concomitant formation of molecular H{sub 2}. This facile reaction pathway involves an attainable transition state of 174.4 kJ/mol. Conversely, competing lower-energy reaction pathways that would lead to the generation of H{sub 2}C{sub 3}S (propadienethione), or C{sub 2}H{sub 2} (acetylene) and CS, involve much more complex, multi-stage pathways, and are not observed experimentally.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1975

Enhanced effects of starlight on the interstellar medium

The photodesorption of molecules and atoms from the surfaces of interstellar grains can be an important source of heating for the interstellar medium and the origin of instabilities which may separate grains and gas. For low densities, the force exerted on the grains is proportional to the gas density and independent of the radiation intensity; for high densities, it is proportional to the radiative flux and independent of the gas density. This force may act differently on grains of different sizes. The photoelectric effect may also be an efficient mechanism for the separation of gas and dust in diffuse clouds.

Gerola, H.↗
NASA NTRS1976

Enhanced effects of starlight on the interstellar medium

The photodesorption of molecules and atoms from the surfaces of interstellar grains can be an important source of heating for the interstellar medium and the origin of instabilities which may separate grains and gas. For low densities, the force exerted on the grains is proportional to the gas density and independent of the radiation intensity; for high densities, it is proportional to the radiative flux and independent of the gas density. This force may act differently on grains of different sizes. The photoelectric effect may also be an efficient mechanism for the separation of gas and dust in diffuse clouds.

Gerola, H.↗
NASA NTRS1991

Modeling the surface and interior structure of comet nuclei using a multidisciplinary approach

The goal was to investigate the structural properties of the surface of comet nucleus and how the surface should change with time under effect of solar radiation. The basic model that was adopted was that the nucleus is an aggregate of frosty particles loosely bound together, so that it is essentially a soil. The nucleus must mostly be composed of dust particles. The observed mass ratios of dust to gas in the coma is never much greater than unity, but this ratio is probably a much lower limit than that of the nucleus because it is vastly easier to remove the gaseous component by sublimation than by carrying off the dust. Therefore the described models assumed that the particles in the soil were frost covered grains of submicron basic size, closely resembling the interstellar grains. The surface properties of such a nucleus under the effects of heating and cooling as the nucleus approaches and recedes from the Sun generally characterized.

Odell, C. R.↗
NASA NTRS1994

Voyager investigation of the cosmic diffuse background: Observations of rocket-studied locations with Voyager

Attachments to this final report include 2 papers connected with the Voyager work: 'Voyager Observations of Dust Scattering Near the Coalsack Nebula' and 'Search for the Intergalactic Medium'. An appendix of 12 one-page write-ups prepared in connection with another program, UVISI, is also included. The one-page write-ups are: (1) Sky survey of UV point sources to 600 times fainter than previous (TD-1) survey; (2) Diffuse galactic light: starlight scattered from dust at high galactic latitude; (3) Optical properties of interstellar grains; (4) Fluorescence of molecular hydrogen in the interstellar medium; (5) Line emission from hot interstellar medium and/or hot halo of galaxy; (6) Integrated light of distant galaxies in the ultraviolet; (7) Intergalactic far-ultraviolet radiation field; (8) Radiation from recombining intergalactic medium; (9) Radiation from re-heating of intergalactic medium following recombination; (10) Radiation from radiative decay of dark matter candidates (neutrino, etc.); (11) Reflectivity of the asteroids in the Ultraviolet; and (12) Zodiacal light.

Henry, Richard C.↗
NASA NTRS2004

The Mineralogy and Grain Properties of the Disk Surfaces in Three Herbig Ae/Be Stars

The ubiquity of accretion disks around pre-main sequence and young main sequence stars having the potential to form planetary systems is now well established. However, unknown is an accurate estimate of the fraction of single stars with disks that have produced planetary systems. Theoretical models of particle aggregation show that if particles can grow from submicron to mm to cm in size, then the formation of planetesimals is possible in the time before the disk dissipates. The problem remains to understand how grains condense from nebular gases, and how relic interstellar grains survive and are modified by their transport in the disk. If grains are lofted above the disk photosphere by processes such as winds, turbulent convection, or changes in vertical structure, the evolution of dust can be investigated by observing the properties of the small (less than or = 1 micron) grains in the optically thin disk surface layer or atmosphere.

Harker, D. E.↗
NASA NTRS1995

Gas-phase chemistry in dense interstellar clouds including grain surface molecular depletion and desorption

We present time-dependent models of the chemical evolution of molecular clouds which include depletion of atoms and molecules onto grain surfaces and desorption, as well as gas-phase interactions. We have included three mechanisms to remove species from the grain mantles: thermal evaporation, cosmic-ray-induced heating, and photodesorption. A wide range of parameter space has been explored to examine the abundance of species present both on the grain mantles and in the gas phase as a function of both position in the cloud (visual extinction) and of evolutionary state (time). The dominant mechanism that removes molecules from the grain mantles is cosmic-ray desorption. At times greater than the depletion timescale, the abundances of some simple species agree with abundances observed in the cold dark cloud TMC-1. Even though cosmic-ray desorption preserves the gas-phase chemistry at late times, molecules do show significant depletions from the gas phase. Examination of the dependence of depletion as a function of density shows that when the density increases from 10(exp 3)/cc to 10(exp 5)/cc several species including HCO(+), HCN, and CN show gas-phase abundance reductions of over an order of magnitude. The CO: H2O ratio in the grain mantles for our standard model is on the order of 10:1, in reasonable agreement with observations of nonpolar CO ice features in rho Ophiuchus and Serpens. We have also examined the interdependence of CO depletion with the space density of molecular hydrogen and binding energy to the grain surface. We find that the observed depletion of CO in Taurus in inconsistent with CO bonding in an H2O rich mantle, in agreement with observations. We suggest that if interstellar grains consist of an outer layer of CO ice, then the binding energies for many species to the grain mantle may be lower than commonly used, and a significant portion of molecular material may be maintained in the gas phase.

Bergin, E. A.↗
NASA NTRS1994

Porphyrins in the interstellar medium (in grains)

Spectral sensitivity of the chromophores to their immediate chemical environment establishes some of the chemical constituents of the grains in which they reside. These are: (1) Paraffins, such as, octane, nonane, decane, and others...(needed for Shpolskii matrices and producing quasilines); and (2) Pyridine. The presence of pyridine is required not only to produce the spectral DIB matching, but also to produce the 36 cm(sup -1) crystal field splitting of the S(sub 1) electronic state. The presence of pyridine in the grains can be confirmed spectroscopically. Pyridine produces a transmission window at 2175 A, matching exactly the well known UV hump. On grain reflection, some of the incoming UV radiation is absorbed into the grain's outer layers. Spikes in the lab and in the astronomical data are due to vibronic transitions in pyridine. The lab spectroscopy reported here clearly establishes the presence of MgTBP, H2TPB, and pyridine in the interstellar grains. The high fluorescence efficiency of MgTBP (being optically pumped in the visible) apparently accounts for all the observed UIR emissions.

Johnson, Fred M.↗
NASA NTRS2009

Insights into the Galactic Cosmic-ray Source from the TIGER Experiment

We report results from 50 days of data accumulated in two Antarctic flights of the Trans-Iron Galactic Element Recorder (TIGER). With a detector system composed of scintillators, Cherenkov detectors, and scintillating optical fibers, TIGER has a geometrical acceptance of 1.7 sq m sr and a charge resolution of 0.23 cu at Iron. TIGER has obtained abundance measurements of some of the rare galactic cosmic rays heavier than iron, including Zn, Ga, Ge, Se, and Sr, as well as the more abundant lighter elements (down to Si). The heavy elements have long been recognized as important probes of the nature of the galactic cosmic-ray source and accelerator. After accounting for fragmentation of cosmic-ray nuclei as they propagate through the Galaxy and the atmosphere above the detector system, the TIGER source abundances are consistent with a source that is a mixture of about 20% ejecta from massive stars and 80% interstellar medium with solar system composition. This result supports a model of cosmic-ray origin in OB associations previously inferred from ACE-CRIS data of more abundant lighter elements. These TIGER data also support a cosmic-ray acceleration model in which elements present in interstellar grains are accelerated preferentially compared with those found in interstellar gas.

Link, Jason T.↗
NASA NTRS1994

Disintegration of Dust Aggregates in Interstellar Shocks and the Lifetime of Dust Grains in the ISM

Interstellar grains are destroyed by shock waves moving through the ISM. In fact, the destruction of grains may be so effective that it is difficult to explain the observed abundance of dust in the ISM as a steady state between input of grains from stellar sources and destruction of grains in shocks. This is especially a problem for the larger grains. Therefore, the dust grains must be protected in some way. Jones et al. have already considered coatings and the increased post-shock drag effects for low density grains. In molecular clouds and dense clouds, coagulation of grains is an important process, and the largest interstellar grains may indeed be aggregates of smaller grains rather than homogeneous particles. This may provide a means to protect the larger grains, in that, in moderate velocity grain-grain collisions in a shock the aggregates may disintegrate rather than be vaporized. The released small particles are more resilient to shock destruction (except in fast shocks) and may reform larger grains later, recovering the observed size distribution. We have developed a model for the binding forces in grain aggregates and apply this model to the collisions between an aggregate and fast small grains. We discuss the results in the light of statistical collision probabilities and grain life times.

Dominik, C.↗
NASA NTRS2000

The Abundances of Solid N2 and Gaseous CO2 in Interstellar Dense Molecular Clouds

We present 2338-2322 per centimeter (4.277-4.307 micrometer) infrared spectra of a number of N2-containing mixed molecular ices and demonstrate that the strength of the infrared "forbidden" band due to the N=N stretch near 2328 per centimeter (4.295 micrometer) is extremely sensitive to the composition of the ice. The strength of the 2328 per centimeter N2 fundamental is significantly enhanced relative to that of pure N2 ice when NH3, H2O, or CO2 are present, but is largely unaffected by the presence of CO, CH4 or O2. We use the laboratory data in coil junction with ISO data that probes several lines-of-sight through dense molecular clouds to place limits on the abundance of interstellar solid phase N2 and the composition of the ices. Deriving upper limits is complicated by the presence of overlapping absorptions due to CO2 gas in the clouds and, in some cases, to photospheric CO in the background star. These upper limits are just beginning to be low enough to constrain interstellar grain models and the composition of possible N2-bearing interstellar ices. We outline the search criteria that will need to be met if solid interstellar N2 is to be detected in the future. We also discuss some of the implications of the presence of warm CO2 gas along the lines-of-sight to embedded protostars and demonstrate that its presence may help resolve certain puzzles associated with the previously derived gas/solid CO2 ratios and the relative abundances of polar and nonpolar ices towards these objects. Finally, we briefly comment on the possible implications of these results for the interpretation of N2 detections on outer solar system bodies.

Sandford, Scott A.↗
NASA NTRS1966

Interstellar molecule formation.

Interstellar molecule formation as result of chemical exchange reactions between atoms of interstellar gas and atoms chemically bound to interstellar grains

INTERSTELLAR MATERIAL↗
DOE OSTI2015

The effect of selective desorption mechanisms during interstellar ice formation

Major components of ices on interstellar grains in molecular clouds—water and carbon oxides—occur at various optical depths. This implies that selective desorption mechanisms are at work. An astrochemical model of a contracting low-mass molecular cloud core is presented. Ice was treated as consisting of the surface and three subsurface layers (i.e., sublayers). Photodesorption, reactive desorption, and indirect reactive desorption were investigated. The latter manifests itself through desorption from H+H reaction on grains. Desorption of shallow subsurface species was also included. Modeling results suggest the existence of a “photon-dominated ice” during the early phases of core contraction. Subsurface ice is chemically processed by interstellar photons, which produces complex organic molecules (COMs). Desorption from the subsurface layer results in high COM gas-phase abundances at A{sub V} = 2.4–10 mag. This may contribute toward an explanation for COM observations in dark cores. It was found that photodesorption mostly governs the onset of ice accumulation onto grains. Reaction-specific reactive desorption is efficient for small molecules that form via highly exothermic atom-addition reactions. Higher reactive desorption efficiency results in lower gas-phase abundances of COMs. Indirect reactive desorption allows for closely reproducing the observed H{sub 2}O:CO:CO{sub 2} ratio toward a number of background stars. Presumably, this can be done by any mechanism whose efficiency fits with the sequence CO⩾CO{sub 2}≫H{sub 2}O. After the freeze-out has ended, the three sublayers represent chemically distinct parts of the mantle. The likely A{sub V} threshold for the appearance of CO ice is 8–10.5 mag. The lower value is supported by observations.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1979

Emission and extinction of ground and vapor-condensed silicates from 4 to 14 microns and the 10 micron silicate feature

Emission and absorption spectra from 4 to 14 microns of ground and laser-vaporized olivine and enstatite silicates are compared with the 10-micron emission feature of the Orion Trapezium. The agreement in band center and shape between the amorphous laser-vaporized olivine sample and the Trapezium feature suggests that amorphous silicate grains of approximately olivine composition may be a major constituent of interstellar dust. Differences between the emission and absorption spectral profiles (absorption plus scattering) show characteristics that could be used as a sensitive probe of the morphology of interstellar grain systems when high signal-to-noise ratio (30-100) observational spectra become available.

Stephens, J. R.↗