The thermal desorption characteristics of 16 astrophysically relevant species from laboratory analogues of the icy mantles on interstellar dust grains have been surveyed in an extensive set of preliminary temperature programmed desorption experiments. The species can be separated into three categories based on behaviour. Water-like species have a single relevant desorption coincident with water. CO-like species show the volcano desorption and co-desorption of trapped molecules, monolayer desorption from the surface of water ice, and multilayer desorption if initially present in sufficient abundance in an outer layer separated from the water ice. Intermediate species show the two desorptions of trapped molecules, and may show a small monolayer desorption for molecules small enough to have a limited ability to diffuse through the structure of porous amorphous water ice. Methods by which the results obtained under laboratory conditions can be adapted for astrophysical situations are discussed.

/pdf/a-laboratory-survey-of-the-thermal-desorption-of-dojmdqhpqm.pdf

A laboratory survey of the thermal desorption of astrophysically relevant molecules

Ices regulate much of the chemistry during star formation and account for up to 80% of the available oxygen and carbon. In this paper, we use the Spitzer c2d Legacy ice survey, complimented with data sets on ices in cloud cores and high-mass protostars, to determine standard ice abundances and to present a coherent picture of the evolution of ices during low- and high-mass star formation. The median ice composition H_(2)O:CO:CO_2:CH_(3)OH:NH_3:CH_4:XCN is 100:29:29:3:5:5:0.3 and 100:13:13:4:5:2:0.6 toward low- and high-mass protostars, respectively, and 100:31:38:4:-:-:- in cloud cores. In the low-mass sample, the ice abundances with respect to H_(2)O of CH_4, NH_3, and the component of CO_2 mixed with H_(2)O typically vary by <25%, indicative of co-formation with H_(2)O. In contrast, some CO and CO_2 ice components, XCN, and CH3OH vary by factors 2-10 between the lower and upper quartile. The XCN band correlates with CO, consistent with its OCN– identification. The origin(s) of the different levels of ice abundance variations are constrained by comparing ice inventories toward different types of protostars and background stars, through ice mapping, analysis of cloud-to-cloud variations, and ice (anti-)correlations. Based on the analysis, the first ice formation phase is driven by hydrogenation of atoms, which results in an H_(2)O-dominated ice. At later prestellar times, CO freezes out and variations in CO freezeout levels and the subsequent CO-based chemistry can explain most of the observed ice abundance variations. The last important ice evolution stage is thermal and UV processing around protostars, resulting in CO desorption, ice segregation, and the formation of complex organic molecules. The distribution of cometary ice abundances is consistent with the idea that most cometary ices have a protostellar origin.

https://iopscience.iop.org/article/10.1088/0004-637X/740/2/109/pdf

The spitzer ice legacy: ice evolution from cores to protostars

Spectra of interstellar CO2 ice absorption features at a resolving power of lambda/Delta lambda approximate to 1500-2000 are presented for 14 lines of sight. The observations were made with the Short-Wavelength Spectrometer (SWS) of the Infrared Space Observatory (ISO). Spectral coverage includes the primary stretching mode of CO2 near 4.27 mu m in all sources; the bending mode near 15.2 mu m is also detected in 12 of them. The selected sources include massive protostars (Elias 29 [in rho Oph], GL 490, GL 2136, GL 2591, GL 4176, NGC 7538 IRS 1, NCC 7538 IRS 9, S140, W3 IRS 5, and W33 A), sources associated with the Galactic Center (Sgr A*, GCS 3 I, and GCS 4), and a background star behind a quiescent dark cloud in Taurus (Elias 16); they thus probe a diverse range of environments. Column densities of interstellar CO2 ice relative to H2O ice fall in the range 10%-23%: this ratio displays remarkably little variation for such a physically diverse sample. Comparison of the observed profiles with laboratory data for CO2-bearing ice mixtures indicates that CO2 generally exists in at least two phases, one polar (H2O dominant) and one nonpolar (CO2 dominant). The observed CO2 profiles may also be reproduced when the nonpolar components are replaced with thermally annealed ices. Formation and evolutionary scenarios for CO2 and implications for grain mantle chemistry are discussed. Our results support the conclusion that thermal annealing, rather than energetic processing due to UV photons or cosmic rays, dominates the evolution of CO2-bearing ices.

/pdf/iso-sws-observations-of-solid-carbon-dioxide-in-molecular-4p0hyw51ty.pdf

ISO-SWS observations of solid carbon dioxide in molecular clouds

We present evidence for several non-ice constituents in the surface material of the icy Galilean satellites, using the reflectance spectra returned by the Galileo near infrared mapping spectrometer (NIMS) experiment. Five new absorption features are described at 3.4, 3.88, 4.05, 4.25, and 4.57 μm for Callisto and Ganymede, and some seem to exist for Europa as well. The four absorption bands strong enough to be mapped on Callisto and Ganymede are each spatially distributed in different ways, indicating different materials are responsible for each absorption. The spatial distributions are correlated at the local level in complex ways with surface features and in some cases show global patterns. Suggested candidate spectrally active groups, perhaps within larger molecules, producing the five absorptions include C-H, S-H, SO2, CO2, and C≡N. Organic material like tholins are candidates for the 4.57- and 3.4-μm features. We suggest, based on spectroscopic evidence, that CO2 is present as a form which does not allow rotational modes and that SO2 is present neither as a frost nor a free gas. The CO2, SO2, and perhaps cyanogen (4.57 μm) may be present as very small collections of molecules within the crystal structure, perhaps following models for radiation damage and/or for comet and interstellar grain formation at low temperatures. Some of the dark material on these surfaces may be created by radiation damage of the CO2 and other carbon-bearing species and the formation of graphite. These spectra suggest a complex chemistry within the surface materials and an important role for non-ice materials in the evolution of the satellite surfaces.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/98JE00788

Non‐water‐ice constituents in the surface material of the icy Galilean satellites from the Galileo near‐infrared mapping spectrometer investigation

Laboratory Studies of the Formation of Methanol and Other Organic Molecules by Water+Carbon Monoxide Radiolysis: Relevance to Comets, Icy Satellites, and Interstellar Ices

Results of measurements of the infrared spectroscopic and condensation-vaporization properties of CO2 in pure and mixed ices are presented. Detailed examination of five infrared CO2 bands, 2.20, 2.78, 4.27, 15.2, and 4.39 microns, shows that the peak position, FWHM, and profile of the bands provide important information about the composition, formation, and subsequent thermal history of the ices. Absorption coefficients and their temperature dependence for all five CO2 bands are determined. The temperature dependence variation is found to be less than 15 percent from 10 to 150 K, i.e., the temperature at which H2O ice sublimes. The number of parameters associated with the physical behavior of CO2 in CO2- and H2O-rich ices, including surface binding energies, and condensation and sublimation temperatures, are determined under experimental conditions. The implications of the data obtained for cometary models are considered.

L. J. Allamandola

Papers

The physical and infrared spectral properties of CO2 in astrophysical ice analogs.