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At least 163 records · Page 9
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NASA NTRS1990

Study of the polyoxymethylene and its sputtered fragments: Implications for comets

Laboratory mass spectra of sputtered polyoxymethylene (POM) reveals a fragmentation pattern consistent with observed peaks in the PICCA experiment on board the Giotto spacecraft. Both commercially available POM and radiation synthesized POM have been used in the studies. Synthesized POM was identified using infrared absorption spectra after proton irradiation of H2CO ice on silicate grains at 20 K. Laboratory results suggest that similar type sputtering is a possible mechanism for removing species from comet grains.

Moore, Marla H.↗
NASA NTRS1990

Interstellar grain chemistry and organic molecules

The detection of prominant infrared absorption bands at 3250, 2170, 2138, 1670 and 1470 cm(-1) (3.08, 4.61, 4.677, 5.99 and 6.80 micron m) associated with molecular clouds show that mixed molecular (icy) grain mantles are an important component of the interstellar dust in the dense interstellar medium. These ices, which contain many organic molecules, may also be the production site of the more complex organic grain mantles detected in the diffuse interstellar medium. Theoretical calculations employing gas phase as well as grain surface reactions predict that the ices should be dominated only by the simple molecules H2O, H2CO, N2, CO, O2, NH3, CH4, possibly CH3OH, and their deuterated counterparts. However, spectroscopic observations in the 2500 to 1250 cm(-1)(4 to 8 micron m) range show substantial variation from source reactions alone. By comparing these astronomical spectra with the spectra of laboratory-produced analogs of interstellar ices, one can determine the composition and abundance of the materials frozen on the grains in dense clouds. Experiments are described in which the chemical evolution of an interstellar ice analog is determined during irradiation and subsequent warm-up. Particular attention is paid to the types of moderately complex organic materials produced during these experiments which are likely to be present in interstellar grains and cometary ices.

Allamandola, L. J.↗
NASA NTRS1990

Laboratory simulation of interstellar grain chemistry and the production of complex organic molecules

During the past 15 years considerable progress in observational techniques has been achieved in the middle infrared (5000 to 500 cm(-1), 2 to 20 microns m), the spectral region most diagnostic of molecular vibrations. Spectra of many different astronomical infrared sources, some deeply embedded in dark molecular clouds, are now available. These spectra provide a powerful probe, not only for the identification of interstellar molecules in both the gas solid phases, but also of the physical and chemical conditions which prevail in these two very different domains. By comparing these astronomical spectra with the spectra of laboratory ices one can determine the composition and abundance of the icy materials frozen on the cold (10K) dust grains present in the interior of molecular clouds. These grains and their ice mantles may well be the building blocks from which comets are made. As an illustration of the processes which can take place as an ice is irradiated and subsequently warmed, researchers present the infrared spectra of the mixture H2O:CH3OH:CO:NH3:C6H14 (100:50:10:10:10). Apart from the last species, the ratio of these compounds is representative of the simplest ices found in interstellar clouds. The last component was incorporated into this particular experiment as a tracer of the behavior of a non-aromatic hydrocarbon. The change in the composition that results from ultraviolet photolysis of this ice mixture using a UV lamp to simulate the interstellar radiation field is shown. Photolysis produces CO, CO2, CH4, HCO, H2CO, as well as a family of moderately volatile hydrocarbons. Less volatile carbonaceous materials are also produced. The evolution of the infrared spectrum of the ice as the sample is warmed up to room temperature is illustrated. Researchers believe that the changes are similar to those which occur as ice is ejected from a comet and warmed up by solar radiation. The warm-up sequence shows that the nitrile or iso-nitrile bearing compound produced during photolysis evaporates between 200 and 250K, suggesting that it is carried by a small molecular species. These molecules could be similar to the source material in Comet Halley that is ejected in grains into the coma, freed by sublimation, and photolyzed by solar radiation to produce the observed jets.

Allamandola, L. J.↗
NASA NTRS1989

Formaldehyde absorption toward W51

Formaldehyde (H2CO) absorption toward the H II region complex W51A (G49.5 - 0.4) in the 6 cm and 2 cm wavelength rotational transitions has been measured with angular resolution of about 0.15 pc. The continuum H II region shows a large, previously undetected shell structure 5.5 pc along the major axis. The absorption, converted to optical depth, shows a higher degree of clumping throughout the map than previous maps at lower resolution; in particular, two narrow regions of enhanced opacity are observed. The absorption in the velocity range 64-67 km/s LSR extends over most of the region, with an observed velocity gradient of 5.2 km/s pc. The opacity structure largely parallels the velocity structure, with a ridge of enhanced opacity to the north of the highest velocity feature. The S/N of the maps allows accurate modeling of the spectral profiles. Nine distinct clumps in the foreground clouds have been identified and parametrized, and column densities for the 1(11) and 2(12) rotational levels of orthoformaldehyde have been derived.

Kogut, A.↗
NASA NTRS1990

In situ measurement of the cosmic microwave background temperature at a distance of 7.5 kiloparsecs

Absorption of orthoformaldehyde (H2CO) toward the giant H II region W51A (G49.5 - 0.4) has been used as a remote probe of the cosmic microwave background (CMB) at a distance of 7.5 kpc. VLA observations of the 6 cm and 2 cm wavelength transitions provided sufficient resolution and sensitivity to resolve condensations within the foregound clouds. Solutions to the equations of statistical equilibrium within each condensation in the context of a large velocity gradient model yielded an estimate for the CMB temperature at 2.1 mm wavelength of 3.2 + or - 0.9 K. The uncertainty is dominated by modeling of collisional pumping by neutral hydrogen molecules (H2).

Kogut, A.↗
NASA NTRS1990

Modeling the chemistry of the dense interstellar clouds. I - Observational constraints for the chemistry

A search for correlations arising from molecular line data is made in order to place constraints on the chemical models of interstellar clouds. At 10 to the 21st H2/sq cm, N(CO) for dark clouds is a factor of six greater than the value for diffuse clouds. This implies that the strength of the UV radiation field where CO shields itself from dissociation is about one-half the strength of the average Galactic field. The dark cloud data indicate that the abundance of CO continues to increase with A(V) for directions with A(V) of 4 mag or less, although less steeply with N(H2) than for diffuse clouds. For H2CO, a quadratic relationship is obtained in plots versus H2 column density. The data suggest a possible turnover at the highest values for A(V). NH3 shows no correlation with H2, C(O-18), HC3N, or HC5N; a strong correlation is found between HC5N and HC3N, indicating a chemical link between the cyanopolyynes.

Federman, S. R.↗
NASA NTRS1989

The evolution of organic mantles on interstellar grains

By laboratory simulation of the chemical processes on dust grains it was investigated how solid organic materials can be produced in the interstellar medium. The ice mantles that accrete on grains in molecular clouds, consisting primarily of H2O, CO, H2CO, NH3, and O2, are irradiated by the internal UV field, resulting in the storage of radicals upon photodissociation of the original molecules. Transient heating events lead to the production of oxygen-rich organic species by recombination reactions. The experiments indicated that in this way the observed amount of organic material can be produced if a grain passes a few times through a molecular cloud during its life. After the destruction of the cloud the grains enter a more diffuse medium. Here they are subjected to the interstellar UV field as well as to collisions with atomic hydrogen. Experiments show that the intense photoprocessing results in the removal of small species like H2O and NH3 as well as in carbonization of the organic molecules. Contrary to this, the atomic H flux will maintain a certain hydrogen level in the mantle. These processes likely convert the original, oxygen-rich organics into an unsaturated hydrocarbon type material such as that observed towards IRS 7 and in Comet Halley grains.

Schutte, Willem A.↗
NASA NTRS1990

Simultaneous imaging of optical CN lines and radio HCN lines in comet Austin

The parent molecule of cometary CN has been the subject of speculation for a long time. When HCN was detected at 3.4 mm in Comet Kohoutek, the problem seemed to be resolved, but much more detailed work on Comet Halley raised the quantitative question of whether HCN could be the only parent. Therefore, comparative CN/HCN studies are vital for understanding the origin of cometary CN. The striking observation of CN jets in Comet Halley raised another very interesting question about the origin of CN. Traditional theory permits only dust features to remain well defined far from the nucleus. The CN jets were interpreted as arising from submicron sized dust particles, perhaps CHON particles. An estimated 10 to 50 percent of the CN in the comet was in the jets in the Halley observations. Several hypotheses can be made: (1) some of the CN originates from the dust and has nothing to do with HCN; or, (2) at least some of the HCN is also produced from the dust in the coma rather than directly from the nucleus. (In the second hypothesis, whether CHN is or is not the parent of the CN associated with the dust would need to be established.) The extended scalelengths found for CO by Eberhardt et. al. (1987) and for H2CO by Snyder et. al. (1989) also support ideas like hypothesis (2). A third hypothesis should be mentioned; contrary to the usual theory, the gas flow does not become isotropic (Combi 1987). For all of the reasons mentioned, it is essential to make a detailed comparison of the spatial distributions of CN and HCN. Furthermore, because of the variability of cometary emissions, it is necessary to make measurements simultaneously.

Palmer, Patrick↗
NASA NTRS1990

The near ultraviolet spectra of comets P/Brorsen-Metcalf and Austin

Results are reported on spectrophotometric observations of comets P/Brorsen-Metcalf and Austin from 3000 to 3600 A at a spectral resolution of about 1.8 A. The strongest features are the OH(A-X) 0-0 and 1-1 bands, and the NH(A-X) 0-0 bands. For the first time, the OH(A-X) 0-1 band was clearly found. The existence of the CN(B-X) 2-1 and 3-2 bands were verified and measured. A feature at 3258 A that was first seen in uncalibrated spectra was detected, and was identified as the NH singlet (c-a) 0-0 transition. The CO2(+) features at 3378, 3504, and 3512 A were also firmly identified. This ion was reported as being present in the tail of Comet Bester (1984 I) by Swings and Page (1950). The identification of a weak feature at 3547 A was proposed as the fundamental transition of H2CO, which would make this the first optical cometary detection of this molecule which is very abundant in giant molecular clouds.

Cochran, William D.↗
NASA NTRS1990

Comet Brorsen-Metcalf in the 3.5 micron region

Comet Brorsen-Metcalf was observed on UT 21 to 24 Aug. 1989 using the CRSP spectrometer and the 1.3 meter telescope at Kitt Peak National Observatory. The cometary continuum was detected on all nights. The data are very noisy, due to the short observation window and the untried nature of the instrument. Low resolution (0.0227 micron) spectra show the 3.4 micron C-H stretch feature having a contrast of at most a factor of two to the neighboring continuum. High resolution (0.0031 micron) spectra between 3.4 and 3.6 microns show 1 sigma features that might be attributed to the nu 5 band of formaldehyde (H2CO). Similar spectra of the region between 3.2 and 3.4 microns show one 3 sigma line at 3.34 microns, which is as yet unidentified. Although the cometary spectra were more spatially extended than the spectra of standard stars, no extension of the line emission beyond the continuum was observed.

Storrs, A. D.↗
NASA NTRS1990

Submillimeter astronomy and low mass star formation

Surveys made at wavelengths shorter than 100 microns are criticized in that they are biased against finding the coldest, most deeply obscured, and possibly youngest protostars. Large scale mapping of star forming regions in the submillimeter continuum and in lines such as CS H2CO and NH3, that are excited at high density, is identified as crucial in order to find clouds in the earliest stages of collapse into stars. The use of photometry from 1 to 1000 microns in characterizing the disks around embedded stars and T Tauri stars is outlined.

Beichman, Charles A.↗
NASA NTRS1990

Mass spectra of sputtered polyoxymethylene - Implications for comets

Laboratory mass spectra of sputtered polyoxymethylene, POM, reveal a mass pattern similar to that detected by the PICCA experiment on board the Giotto spacecraft. Both commercially available POM and radiation-synthesized POM have been used in the studies. Synthesized POM was identified by its infrared absorption spectra after proton irradiation of H2CO condensed on silicate grains at 20 K. Laboratory results suggest that a similar type of sputtering is a possible mechanism for removing species from cometary grains.

Moore, Marla H.↗
NASA NTRS1991

Dust and molecular properties of the low-opacity cloud Lynds 1563

Optical, molecular, and far-infrared data are analyzed for L1563, estimated peak Ab 2.5 mag. The cloud is detected by IRAS at 12, 25, 60, and 100 microns, and with CO, (C-13)O, and H2CO molecules. A column density comparison yields an estimate of the temperature of the classical dust grains of 15.6 + or - 1 K, while the color temperature derived from the ratio I(60)/I(100) is 26 K. Both dust and color temperatures decrease toward the cloud center.

Clark, Frank O.↗
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.↗