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At least 181 records · Page 10
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NASA NTRS1991

Detection of solid methanol toward W33A

A recently detected absorption feature at 3.53 microns in the spectrum of W33A has been assigned to methanol (CH3OH). Its optical depth implies that methanol is the second most abundant molecule (7 percent relative to H2O) in the grain mantles in the line of sight toward W33A observed to date. Laboratory experiments have shown that the implied abundance is difficult to explain by UV irradiation of the dust grains alone. Grain surface reactions or condensation directly out of the gas phase must also play roles, but the relative contributions of the various processes are difficult to estimate. The optical depth of the 3.53-micron feature constrains the contribution of methanol to the 6.8-micron feature in W33A to be 10 percent or less, requiring the contribution of at least one other compound to this feature, while the estimated contribution to the 4.9-micron absorption band is even smaller. Only a small contribution of formaldehyde (H2CO) is consistent with the observed 3.53-micron band profile. In contrast to methanol, formaldehyde can be produced readily by photochemical reactions within the ice mantle.

Grim, R. J. A.↗
NASA NTRS1991

Interpretation of the ion mass spectra in the mass per charge range 25-35 amu/e obtained in the inner coma of Halley's comet by the HIS-sensor of the Giotto IMS experiment

The IMS-HIS double-focusing mass spectrometer that flew on the Giotto spacecraft covered the mass per charge range from 12 to 56 (amu/e). By comparing flight data, calibration data and results of model calculations of the ion population in the inner coma, the absolute mass scale is established, and ions in the mass range 25 to 35 are identified. Ions resulting from protonation of molecules with high proton affinity are relatively abundant, enabling us to estimate relative source strengths for H2CO, CH3OH, HCN, and H2S, providing for the first time a positive in situ measurement of methanol. Also, upper limits for NO and some hydrocarbons are derived.

Geiss, J.↗
NASA NTRS1991

Laboratory and observational study of the interrelation of the carbonaceous component of interstellar dust and solar system materials

By studying the chemical and isotopic composition of interstellar ice and dust, one gains insight into the composition and chemical evolution of the solid bodies in the solar nebula and the nature of the material subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to spectroscopically probe the composition of interstellar ice and dust in the mid-infrared, the spectral range which is most diagnostic of fundamental molecular vibrations. We can compare these spectra of various astronomical objects (including the diffuse and dense interstellar medium, comets, and the icy outer planets and their satellites) with the spectra of analogs we produce in the laboratory under conditions which mimic those in these different objects. In this way one can determine the composition and abundances of the major constituents of the various ices and place general constraints on the types of organics coating the grains in the diffuse interstellar medium. In particular we have shown the ices in the dense clouds contain H2O, CH3OH, CO, perhaps some NH3 and H2CO, we well as nitriles and ketones or esters. Furthermore, by studying the photochemistry of these ice analogs in the laboratory, one gains insight into the chemistry which takes place in interstellar/precometary ices. Chemical and spectroscopic studies of photolyzed analogs (including deuterated species) are now underway. The results of some of these studies will be presented and implications for the evolution of the biogenic elements in interstellar dust and comets will be discussed.

Allamandola, L. J.↗
NASA NTRS1991

Kinetic conversion of CO to CH4 in the Solar System

Some of the most interesting chemistry in the Solar System involves changes in the oxidation state of the simple carbon species. The chemical pathways for the conversion of CH4 to CO and CO2 are for the most part known. The reverse process, the reduction of CO to CH4, is, however, poorly understood. This is surprising in view of the importance of the reduction process in the chemistry of the Solar System. Recently we investigated the chemical kinetics of a hitherto unsuspected reaction. It is argued that the formation of the methoxy radical (CH3O) from H+H2CO may play an essential role in the reduction of CO to CH4. The rate coefficient for this reaction has been estimated using the approximate theory of J. Troe and transition state theory. We will discuss the implications of this reaction for the chemistry of CO on Jupiter, in the solar nebula, for interpreting the laboratory experiments of A. Bar-Nun and A. Shaviv and A. Bar-Nun and S. Chang, and for organic synthesis in the prebiotic terrestrial atmosphere. The possible relation of CO reduction in the solar nebula and polyoxymethylene observed in comet Halley will be discussed.

Yung, Y. L.↗
NASA NTRS1991

The relative importance of prebiotic synthesis on the Earth and input from comets and meteorites

The prebiotic synthesis of hydrogen cyanide and formaldehyde was studied by the action of electric discharges on various model primitive atmospheres containing CH4, CO, and CO2. Photochemical production rates would also have been important and were calculated for HCN and H2CO. A reasonable rate of synthesis of amino acids from these sources is about 10 n moles/(sq cm yr) or 0.10 moles/sq cm in 10(exp 7) yrs. This would give a concentration of 3 x 10(exp -4) M in an ocean of the present size (300 liters/sq cm). The amino acids cannot accumulate over a longer period because the entire ocean passes through the 350 C submarine vents in 10(exp 7) yrs, which decomposes all the organic compounds. A number of workers have calculated the influx of comets and meteorites on the primitive earth, both as a destructive process for organic compounds and for any life that was present, as well as a source of organic compounds. Some of the amino acids from the meteorite proposed to have hit the earth 65 x 10(exp 6) yrs ago were detected at the Cretaceous/Tertiary boundary sediments. The problem with proposing a large scale input of organic compounds from meteorites and comets is that they must survive passage through the atmosphere and impact. There are some processes that would allow survival such as showers of centimeter to meter sized meteorites and various aerodynamic braking processes for larger objects. Even if a significant amount of the organic material survived impact, the destructive processes in the hydrothermal vents would remove these compounds on the average in 10(exp 7) yrs or less. If it is assumed that the input rate was sufficient to overcome these destructive processes, then too much carbon and water, especially from comets, would have been added to the surface of the earth. It was concluded that while some organic material was added to the earth from comets and meteorites, the amount available from these sources at a given time was only a few percent of that from earth based syntheses.

Miller, S. L.↗
NASA NTRS1992

Near-ultraviolet spectroscopy of Comet Austin (1989c1)

Comet Austin (1989c1) was observed post-perihelion at a heliocentric distance near 1.25 AU. The wavelength range was from the atmospheric cutoff at 3000 to 4000 A. The coma spectra were calibrated into flux units and the contaminating sky spectrum and solar scattered light continuum were subtracted, leaving an ultraviolet spectrum of about 1.5-A resolution and excellent signal-to-noise ratio. The spectrum is dominated by emissions from OH, NH, CH, C3, and CN, some of the weaker emissions of which are seen here for the first time. More bands of CO(2+) were found than in any previous investigation and several intensity anomalies were noted; H2CO, OH(+), NCN, N(2+), and CN(+) may be present. Several emission features well above the noise level remain unidentified. The relative intensities of the OH and CN bands agree with the predictions of resonance fluorescence when one considers the potential effects of contamination by other molecules. The effects of the ozone absorption spectrum are not fully removed by the data-reduction process, although this does not affect these results.

Valk, Jacobus H.↗
NASA NTRS1991

Interpretation of the ion mass spectra in the mass range 25-35 obtained in the inner coma of Halley's comet by the HIS-sensor of the Giotto IMS Experiment

The IMS-HIS double-focussing mass spectrometer that flew on the Giotto spacecraft covered the mass per charge range from 12 to 56 (AMU/e). By comparing flight data, calibration data, and results of model calculations of the ion population in the inner coma, the absolute mass scale is established, and ions in the mass range 25 to 35 are identified. Ions resulting from protonation of molecules with high proton affinity are relatively abundant, enabling us to estimate relative source strengths for H2CO, CH3OH, HCN, and H2S, providing for the first time a positive in situ measurement of methanol. Also, upper limits for NO and some hydrocarbons are derived.

Geiss, J.↗
NASA NTRS1993

Computed Potential Energy Surfaces for Chemical Reactions

A manuscript describing the calculations on the (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO product channels in the CH3 + OH reaction, which were described in the last progress report, has been accepted for publication in J. Chem. Phys., and a copy of the manuscript is included in the appendix. The production of (1)CH2 in this reaction is important in hydrocarbon combustion since (1)CH2 is highly reactive and would be expected to insert into N2, possibly leading to a new source for prompt NO(x) (vide infra). During the last six months new calculations have been carried out for the NH2 + NO system, which is important in the thermal de-NO(x) process.

Heinemann, K.↗
NASA NTRS1992

Observations of cometary parent molecules with the IRAM radio telescope

Several rotational transitions of HCN, H2S, H2CO, and CH3OH were detected in comets P/Brorsen-Metcalf 1989 X, Austin (1989c1) and Levy (1990c) with the Institute for Millimeter Radioastronomy (IRAM) 30-m radio telescope. This allows us to determine the production rates of these molecules and to probe the physical conditions of the coma.

Colom, P.↗
NASA NTRS1991

Carbonaceous compounds in comets - Infrared observations

The Comet Halley observations showed that carbon is a major component of the comet nucleus, with mass spectroscopic data giving near-cosmic C/O ratios. Gaseous and solid compounds were also observed with infrared spectroscopy, which gave detections of CO and CO2, probable detections or upper limits of H2CO and CH4, and a tentative detection of OCS. The CH4/CO ratio of less than unity in Comet Halley points to a CO-rich solar nebula; however, the ratio is higher than in interstellar clouds. A broad, complicated emission feature near 3.4 microns is evidence for carbonaceous compounds containing C-H groups in gas or solid phases. Analysis of radiation mechanisms and abundance constraints suggests that thermal emission or transient heating by single photons can account for the 3.4-micron emission feature. The band resembles (but is not identical to) bands of carbonaceous chondrite organic material, synthetic materials, and interstellar carbonaceous bands.

Encrenaz, T.↗
NASA NTRS1991

A review of radio interferometric imaging of comets

An overview of cometary observations carried out with the VLA which include OH imaging observations, studies of other molecules, and searches for continuum emission, is presented. Attention is focussed on the OH observations obtained of Comet Halley, a periodic comet, and Comet Wilson, a 'new' comet. The emission from Comet Halley is confined to a region a few times 10 exp 5 km. The emission from Comet Wilson exhibits sporadic blobs at large distances (about 10 exp 6 from the center), which vary abruptly in both position and velocity. It is suggested that for Comet Halley, collisional effects near the edge of the quenching region, which is coincidentally the approximate distance to the cometopause, may be important, and that for Comet Wilson, outgassing from cometesimals ejected from the nucleus may be significant. It is shown that asymmetric line profiles are more common than previously thought. H2CO detection experiments for comets Halley and Machholz are summarized.

De Pater, Imke↗
NASA NTRS1992

Tests of shock chemistry in IC 443G

Eight molecular species, in the hot dense clump IC 443G, believed to be impacted by the shock wave from the SNR IC 443, are investigated. The clump consists of two distinct regions, one relatively cool, and one hotter and denser. Region 1 contains CO, HCO(+), HCN, and CN, whose abundances may be explained either by ion-molecule chemistry, or by a D shock of 60-90 km/s, passing through a clump of about 100,000/cu cm. Region 2 gives rise to SiO, CS, SO, and H2CO, and requires an ND shock of 5-15 km/s passing through a region of about 1,000,000/cu cm. Observed fractional abundances fit ND shock models if L is about 6.6 x 10 exp 15 cm. In general, observed line widths vary inversely with derived excitation density, while centroid velocities of all species are essentially identical.

Turner, B. E.↗
NASA NTRS1992

Infrared spectroscopic measurements of tropospheric trace gases

Absorption features of several trace gases have been detected in 0.017-cm-resolution infrared spectra recorded over surface-level paths of 0.5 and 1.5 km at the National Solar Observatory on Kitt Peak, near Tucson, Arizona. Measurements of O3, HCOOH, NH3, and H2CO are briefly discussed.

Rinsland, Curtis P.↗
NASA NTRS1993

The observation of correlated velocity structures in a translucent molecular cloud and implications for turbulence

We present a formaldehyde map of the translucent high-latitude molecular cloud MBM 16. The molecular gas traced by the H2CO is located in spatially distinct large structures that exhibit velocity coherence on a scale of 0.5 pc. These structures are not pressure-confined and are probably not self-gravitating. They may be transient structures. If so, we suggest that they are produced by shear flows whose scale length is of order the size of the cloud.

Magnani, L.↗
NASA NTRS1993

Evidence for protostellar collapse in B335

We have observed five rotational transitions of H2CO and CS toward the Bok globule, B335, with high spatial and spectral resolution. The characteristic shape of the observed profiles provides direct, kinematic evidence of collapse. In addition, we have modeled line profiles of collapsing dense cores with density and velocity structures taken from the theory of Shu and coworkers. Using the age of collapse as the only free parameter, we found that the strengths and profiles of the observed lines can be well fitted by the theoretical model. Our best-fit model gives an age of 1.5 x 10 exp 5 yr, corresponding to an infall radius of 0.04 pc and a total mass of 0.4 solar mass for the central star and disk. Outside the infall radius, there is a static envelope with a r exp -2 density distribution, an average temperature of 13 K, and a turbulent velocity (1/e width) of 0.12 km/s. The CS abundance is 3.6 x 10 exp -9 with about 30 percent uncertainty.

Zhou, Shudong↗
NASA NTRS1991

Theoretical molecular studies of astrophysical interest

When work under this grant began in 1974 there was a great need for state-to-state collisional excitation rates for interstellar molecules observed by radio astronomers. These were required to interpret observed line intensities in terms of local temperatures and densities, but, owing to lack of experimental or theoretical values, estimates then being used for this purpose ranged over several orders of magnitude. A problem of particular interest was collisional excitation of formaldehyde; Townes and Cheung had suggested that the relative size of different state-to-state rates (propensity rules) was responsible for the anomalous absorption observed for this species. We believed that numerical molecular scattering techniques (in particular the close coupling or coupled channel method) could be used to obtain accurate results, and that these would be computationally feasible since only a few molecular rotational levels are populated at the low temperatures thought to prevail in the observed regions. Such calculations also require detailed knowledge of the intermolecular forces, but we thought that those could also be obtained with sufficient accuracy by theoretical (quantum chemical) techniques. Others, notably Roy Gordon at Harvard, had made progress in solving the molecular scattering equations, generally using semi-empirical intermolecular potentials. Work done under this grant generalized Gordon's scattering code, and introduced the use of theoretical interaction potentials obtained by solving the molecular Schroedinger equation. Earlier work had considered only the excitation of a diatomic molecule by collisions with an atom, and we extended the formalism to include excitation of more general molecular rotors (e.g., H2CO, NH2, and H2O) and also collisions of two rotors (e.g., H2-H2).

Flynn, George↗
NASA NTRS1994

Identification of a collapsing protostar

The globular molecular cloud B335 contains a single, deeply embedded, far-infrared source. Our recent observations of H2CO and CS lines toward this source provide direct kinematic evidence for collapse. Both the intensity and detailed shape of the line profiles match those expected from inside-out collapse inside a radius of 0.036 pc. The collapse began about 1.5 X 10(exp 5) years ago, similar to the onset of the outflow. The mass accretion rate is about 10 times the outflow rate, and about 0.4 solar mass should have now accumulated in the star and disk. Because B335 rotates only very slowly, any disk would still be very small (about 3 AU). The accretion luminosity should be adequate to power the observed luminosity. Consequently, we believe that B335 is indeed a collapsing protostar.

Evans, Neal J., II↗
NASA NTRS1994

The nature of the source of CO in Comet P/Halley

We show by numerical simulations that the CO distribution in the coma of Comet P/Halley as measured by neutral gas mass spectrometer aboard Giotto spacecraft (P. Eberhardt et al., 1987) can be explained by an extended jet source originating from vent 1 in the rotational model of M. J. S. Belton et al. (1991). This is an alternative interpretation for the origin of the CO distribution where Eberhardt et al. (1987) explained the observations in terms of a spherically symmetric extended source function. We still find nearly 1/3 of CO is due to CO sublimating directly at the nucleus, possibly from the vent itself. Approximately 50% of CO that originates in the extended jet source may be formed via photolysis of H2CO while the rest can be due to CO trapped in grain mantels and other C=O-bearing molecules. The overall production rates of CO in the two models differ by less than 29%. The prediction of the jet source model compares satisfactorily with the distribution of CO observed in the coma by the IUE satellite but unfortunately does not allow one to discriminate between the two models.

Samarasinha, Nalin H.↗