Search

Spectra and optical constants of nitrile ices known or suspected to be in Titan?s atmosphere have been determined from 2.0 to 333.3 microns (approx.5000 to 30/cm). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan?s winter pole. Ices studied were: HCN, hydrogen cyanide; C2N2, cyanogen; CH3CN, acetonitrile; C2H5CN, propionitrile; and HC3N, cyanoacetylene. Optical constants were calculated, using Kramers-Kronig analysis, for each nitrile ice?s spectrum measured at a variety of temperatures, in both the amorphous- and crystalline phases. Spectra were also measured for many of the nitriles after quenching at the annealing temperature and compared with those of annealed ices. For each of these molecules we also measured the real component, n, of the refractive index for amorphous and crystalline phases at 670 nm. Several examples of the information contained in these new data sets and their usefulness in modeling Titan?s observed features will be presented (e.g., the broad emission feature at 160/cm; Anderson and Samuelson, 2011).

Astronomical observations of the past few decades have revealed the existence of a variety of molecules in extraterrestrial ices. These molecules include H2O, CO, and CO2, and organics such as CH4, CH30H, and C2H6. Some ices are dominated by polar molecules, while non-polar species appear to dominate others. Observations, mainly in the radio and IR regions, have allowed the inference of other solid-phase molecules whose formation remains difficult to explain by gas-phase chemistry alone. Several laboratory research groups have reported on extensive experiments on the solid-phase reaction chemistry of icy materials, generally as initiated by either ionizing radiation or vacuum-UV photons. These experiments not only permit molecular identifications to be made from astronomical observations, but also allow predictions of yet unidentified molecules. This laboratory approach has evolved over more than 30 years with much of the earliest work focusing on complex mixtures thought to represent either cometary or interstellar ices. Although those early experiments documented a rich solid-state photo- and radiation chemistry, they revealed few details of reactions for particular molecules, partly due to the multi-component nature of the samples. Since then, model systems have been examined that allow the chemistry of individual species and specific reactions to be probed. Reactions involving most of the smaller astronomical molecules have now been studied and specific processes identified. Current laboratory work suggests that a variety of reactions occur in extraterrestrial ices, including acid-base processes, radical dimerizations, proton transfers, oxidations, reductions, and isomerizations. This workshop presentation will focus on chemical reactions relevant to solar system and interstellar ices. While most of the work will be drawn from that to which the speaker has contributed, results from other laboratories also will be included. Suggestions for future studies will be made, with an emphasis on some present deficiencies. The speaker's work has been generously supported by these NASA research programs: Cassini Data Analysis, Exobiology, Mars Fundamental Research, Outer Planets Research, Planetary Atmospheres, Planetary Geology and Geophysics, and the NASA Astrobiology Institute.

Oort Cloud comets, as well as TNOs Makemake (2045 FYg), Quaoar, and Pluto, are known to contain ethane. However, even though this molecule is found on several outer Solar System objects relatively little information is available about its amorphous and crystalline phases. In new experiments, we have prepared ethane ices at temperatures applicable to the outer Solar System, and have heated and ion-irradiated these ices to study phase changes and ethane's radiation chemistry using mid-IR spectroscopy (2.2 - 16.6 microns). Included in our work is the meta-stable phase that exists at 35 - 55 K. These results, including newly obtained optical constants, are relevant to ground-based observational campaigns, the New Horizons mission, and supporting laboratory work. An improved understanding of solid-phase ethane may contribute to future searches for this and other hydrocarbons in the outer Solar System.

Astronomical observations of both solar system and interstellar regions have revealed a rich chemical inventory that includes most classes of organic molecules and selected inorganics. For example, gas-phase ethylene glycol and SOz have been observed by astronomers, while solidphase detections include OCS, H2O2 , and the cyanate anion.' All of these are found in environments that are, by earthly standards, exceedingly hostile: temperatures of 10 - 100 K, miniscule densities, and near-ubiquitous ionizing-radiation fields. Beyond the simplest chemical species, these conditions have made it difficult-to-impassible to account for the observed molecular abundances using gas-phase chemistry, suggesting solid-phase reactions play an important role. In extraterrestrial environments, cosmic rays, UV photons, and magnetospheric radiation all drive chemical reactions, even at cryogenic temperatures. To study this chemistry, radiation astrochemists conduct experiments on icy materials, frozen under vacuum and exposed to sources such as keV electrons and MeV protons. Compositional changes usually are followed with IR spectroscopy and, in selected cases, more-sensitive mass-spectral techniques. This talk will review some recent results on known and suspected extraterrestrial molecules and ions. Spectra and reaction pathways will be presented, and predictions made for interstellar chemistry and the chemistry of selected solar system objects. Some past radiation-chemical contributions, and future needs, will be explored.

More than 140 gas-phase molecules have been detected in the interstellar (IS) medium or in circumstellar environments including inorganics, organics, ions, and radicals. The significant abundance of large, complex organic molecules, and families of isomers in these regions makes the origin and formation history of these species the subject of debate. Observationally determined condensed-phase species are H2O, CO, CO2, NH3 and CH30H, with CH4, HCOOH, OCS, OCN-, H2CO and NH4(+) present at trace levels. These ices can undergo energetic processing with cosmic rays or far-UV photons to form larger complex organics with abundance levels that make them undetectable in icy mantles. Once warmed, however, it is likely that these complex species would enter the gas-phase where they might be detected by Herschel or Alma. Understanding the role of radiation chemistry and thermal processing of ices and identifying new products are the goals of our laboratory research. In the Cosmic lee Laboratory at NASA Goddard Space Plight Center, we can study both the photo-and radiation chemistries of ices from 8 -- 300 K. Using dear- and mid-IR spectroscopy we can follow the destruction of primary molecules and the formation of radicals and secondary products as a function of energetic processing. During warming we can monitor the trapping of species and the results of any thermal chemistry. An overview of recent and past work will focus on complex secondary radiation products from small condensed-phase IS species. Likely reactions include dimerization, isomerization, H-addition and H-elimination. Another focus of our work is the development of reaction schemes for the formation of complex molecules and the use of such schemes to predict new molecules awaiting detection by Herschel and Alma.

Ozone, O3, has been observed on the surfaces of Ganymede and the Saturnian satellites Dione and Rhea. It is generally accepted that in each case the O3 is formed by the magnetospheric irradiation of oxygen, O2, within water-rich icy surfaces. Carbon dioxide ice, which has been detected on a number of planetary-satellite surfaces, is another possible source of O3 after irradiation. Laboratory work to date has focused on O3 formation from irradiated O2 at 10 K using < 1O eV and 5 keV electrons and 100 keV protons. The temperature-dependent formation of O3 in solid O2 from 11 to 30 K using 5 keV electrons also has been examined. The objectives of the present laboratory study are (1) to compare O3 formation in O2 and CO2 ices using MeV proton and 10 keV electron bombardment at different temperatures, and (2) to examine ozone's thermal stability in different icy matrices (O2, CO2, H2O) during warming. Our results will aid in the understanding of these possible abiotic ozone sources, which is necessary when assessing O3 as a potential biomarker.

Polar, heliophysical, and planetary science topics related to the International Heliophysical and Polar Years 2007-2009 were addressed during this circumpolar video conference hosted January 23-29, 2808 at the new Barrow Arctic Research Center of the Barrow Arctic Science Consortium in Barrow, Alaska. This conference was planned as an IHY-IPY event science outreach event bringing together scientists and educational specialists for the first week of sunrise at subzero Arctic temperatures in Barrow. Science presentations spanned the solar system from the polar Sun to Earth, Moon, Mars, Jupiter, Saturn, and the Kuiper Belt. On-site participants experienced look and feel of icy worlds like Europa and Titan by being in the Barrow tundra and sea ice environment and by going "on the ice" during snowmobile expeditions to the near-shore sea ice environment and to Point Barrow, closest geographic point in the U.S. to the North Pole. Many science presentations were made remotely via video conference or teleconference from Sweden, Norway, Russia, Canada, Antarctica, and the United States, spanning up to thirteen time zones (Alaska to Russia) at various times. Extensive educational outreach activities were conducted with the local Barrow and Alaska North Slope communities and through the NASA Digital Learning Network live from the "top of the world" at Barrow. The Sun- Earth Day team from Goddard, and a videographer from the Passport to Knowledge project, carried out extensive educational interviews with many participants and native Inupiaq Eskimo residents of Barrow. Video and podcast recordings of selected interviews are available at http://sunearthday.nasa.gov/2008/multimedidpodcasts.php. Excerpts from these and other interviews will be included in a new high definition video documentary called "From the Sun to the Stars: The New Science of Heliophysics" from Passport to Knowledge that will later broadcast on NASA TV and other educational networks. Full conference proceedings are accessible at http://polargateways2008.org/.

Hydrogen peroxide has been identified on Europa (Carlson et al. 1999) based in part on the 3.50 micron absorption feature observed in Galileo NIMS spectra. The observed feature was fitted with laboratory reflectance spectra of H2O + H2O2. Since condensed phase molecules on Europa (H2O, CO2, SO2, and H2O2) are bombarded with a significant flux of energetic particles (H(+), O(n+), S(n+) and e-), we examined the proton irradiation of H2O at 80 K and the conditions for the IR detection of H2O2 near 3.5 microns. Contrary to expectations, H2O2 was not detected if pure H2O ice was irradiated at 80 K. This was an unexpected result since, H2O2 was detected if pure H2O was irradiated at 18 K. We find, however, that if H2O ice contains either O2 or CO2 then H2O2 is detected after irradiation at 80 K (Moore and Hudson, 1999). The source of O2 for the H2O ice on Europa could come from surface interactions with the tenuous oxygen atmosphere, or from the bombardment of the surface by O(n+).

Infrared spectra of H2O, CH3OH, and NH3 condensed at T less than 20 K on amorphous silicate smokes reveal that predominantly crystalline phase ice forms directly on deposit. Spectra of these molecules condensed on aluminum substrates at T less than 20 K indicate that amorphous phase ice forms. On aluminum, crystalline phase H2O and CH3OH are formed by annealing amorphous deposits to 155 K and 130 K, respectively (or by direct deposit at these temperatures); crystalline NH3 is formed by direct deposit at 88 K. Silicate smokes are deposited onto aluminum substrates by evaporation of SiO solid or by combustion of SiH4 with O2 in flowing H2 followed by vapor phase nucleation and growth. Silicate smokes which are oxygen-deficient may contain active surface sites which facilitate the amorphous-to-crystalline phase transition during condensation. Detailed experiments to understand the mechanism are currently in progress. The assumption that amorphous phase ice forms routinely on grains at T less than 80 K is often used in models describing the volatile content of comets or in interpretations of interstellar cloud temperatures. This assumption needs to be reexamined in view of these results.

Observations of nonterrestrial clathrate hydrates are still lacking despite the fact that clathrates first were suggested to exist in cometary and interstellar ices over 40 years ago. Spectroscopy, the most direct method of astronomical detection, has been hampered by the similarity of clathrate hydrate spectra to those of unenclathrated guest molecules and solid H2O. We have prepared a methanol (CH3OH) clathrate hydrate, using a recently published procedure, and have investigated its far-infrared spectrum. The spectrum is quite different from that of either unenclathrated CH3OH or solid H2O and so should be of value in astronomical searches for this clathrate.

Changes in the FIR spectrum of crystalline and amorphous water ice as a function of temperature are reported. The dramatic differences between the spectra of these ices in the FIR are used to examine the effect of proton irradiation on the stability of the crystalline and amorphous ice phases from 13 to 77 K. In particular, the spectra near 13 K show interconversion between the amorphous and crystalline ice phases beginning at doses near 2 eV/molecule and continuing cyclically with increased dose. The results are used to estimate the stability of irradiated ices in astronomical environments.

Far infrared spectra from 20 microns (500 cm(sup -1)) to 100 microns (100 cm(sup -1)) of water ice were measured. Amorphous ice deposited at 13 K has one absorption band at 45 microns (220 cm(sup -1)). Amorphous ice evolves into a crystalline form with absorptions at 44 microns (229 cm(sup -1)) and 62 microns (162 cm(sup -1)) as the temperature is increased to 155 K. Spectra documenting this phase change are presented as well as spectra of crystalline ice at temperatures between 13 K and 155 K. Far infrared spectra of amorphous and crystalline water ice before and after proton irradiation are also presented. Changes in these two forms are discussed in relation to ices in comets, grains, and planetary satellites in various radiation environments. Observations of non-terrestrial clathrate hydrates are still lacking despite the fact that clathrates first were suggested to exist in cometary and interstellar ices over forty years ago. Spectroscopy, the most direct method of astronomical detection, has been hampered by the similarity of clathrate hydrate spectra to those of unenclathrated guest molecules and solid H2O. A methanol (CH3OH) clathrate hydrate, using a recently published procedure, was prepared and its far-IR spectrum investigated. The spectrum is quite differenct from that of either unenclathrated CH3OH or solid H2O and so should be of value in astronomical searches for this clathrate.

It has been experimentally shown that the position of the -SiH fundamental vibrational stretch is very sensitive to the chemical environment surrounding the Si atom. Si in an oxidizing environment will display an -SiH feature near 4.4 microns, whereas Si in a reducing grain could be responsible for a feature at 4.74 microns. It is further shown that, as an oxidized grain is reduced, the -SiH fundamental shifts to longer wavelengths through a series of intermediate bands.

The infrared spectra of amorphous silicate grains and films formed in a variety of laboratory experiments have been measured. It is found that the frequency of the SiH fundamental stretch is extremely sensitive to the chemical environment of the grain in which the silicon is bound and varies from 2270/cm in oxidized grains to 2110/cm in a reducing environment. It is proposed that features previously observed in W33A could be due to -SiH groups in amorphous silica, partially reduced silica, silicon nitride or slightly oxidized silicon carbide. It is predicted that observations at 2270/cm will reveal a feature due to -SiH groups in highly oxidized interstelar and circumstellar grains. Such a feature might also appear in the spectra of 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.

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.

Results from experimental studies of the irradiation of SiH4-H2O and Fe(CO)5-SiH4-H2O ice mixtures at 15 K using 1 MeV protons have revealed the synthesis of a very stable infrared spectral feature at 4.6 microns which is characteristic of the SiH functional group. This feature persists through warmup of the ice, exposure to air at 300 K, and vacuum annealing to at least 400 K. Because of the high cosmic abundance of both silicon and hydrogen and the unexpected stability of the SiH feature in our experiments, it is suggested that SiH might be responsible for the 4.6 micron absorption feature observed in W33A.