Vacuum-UV spectroscopy of interstellar ice analogs. II. Absorption cross-sections of nonpolar ice molecules

Dust grains in cold circumstellar regions and dark-cloud interiors at 10-20 K are covered by ice mantles. A nonthermal desorption mechanism is invoked to explain the presence of gas-phase molecules in these environments, such as the photodesorption induced by irradiation of ice due to secondary ultraviolet photons. To quantify the effects of ice photoprocessing, an estimate of the photon absorption in ice mantles is required. In a recent work, we reported the vacuum-ultraviolet (VUV) absorption cross sections of nonpolar molecules in the solid phase. The aim was to estimate the VUV-absorption cross sections of nonpolar molecular ice components, including CH4, CO2, N2, and O2. The column densities of the ice samples deposited at 8 K were measured in situ by infrared spectroscopy in transmittance. VUV spectra of the ice samples were collected in the 120-160 nm (10.33-7.74 eV) range using a commercial microwave-discharged hydrogen flow lamp. We found that, as expected, solid N2 has the lowest VUV-absorption cross section, which about three orders of magnitude lower than that of other species such as O2, which is also homonuclear. Methane (CH4) ice presents a high absorption near Ly-alpha (121.6 nm) and does not absorb below 148 nm. Estimating the ice absorption cross sections is essential for models of ice photoprocessing and allows estimating the ice photodesorption rates as the number of photodesorbed molecules per absorbed photon in the ice.Comment: 9 pages, 6 figures, 7 table

Investigation of HNCO isomers formation in ice mantles by UV and thermal processing: an experimental approach

Current gas phase models do not account for the abundances of HNCO isomers detected in various environments, suggesting a formation in icy grain mantles. We attempted to study a formation channel of HNCO and its possible isomers by vacuum-UV photoprocessing of interstellar ice analogues containing H$_2$O, NH$_3$, CO, HCN, CH$_3$OH, CH$_4$, and N$_2$ followed by warm-up, under astrophysically relevant conditions. Only the H$_2$O:NH$_3$:CO and H$_2$O:HCN ice mixtures led to the production of HNCO species. The possible isomerization of HNCO to its higher energy tautomers following irradiation or due to ice warm-up has been scrutinized. The photochemistry and thermal chemistry of H$_2$O:NH$_3$:CO and H$_2$O:HCN ices was simulated using the Interstellar Astrochemistry Chamber (ISAC), a state-of-the-art ultra-high-vacuum setup. The ice was monitored in situ by Fourier transform mid-infrared spectroscopy in transmittance. A quadrupole mass spectrometer (QMS) detected the desorption of the molecules in the gas phase. UV-photoprocessing of H$_2$O:NH$_3$:CO/H$_2$O:HCN ices lead to the formation of OCN$^-$ as main product in the solid state and a minor amount of HNCO. The second isomer HOCN has been tentatively identified. Despite its low efficiency, the formation of HNCO and the HOCN isomers by UV-photoprocessing of realistic simulated ice mantles, might explain the observed abundances of these species in PDRs, hot cores, and dark clouds

Nature and evolution of the dominant carbonaceous matter in interplanetary dust particles: effects of irradiation and identification with a type of amorphous carbon

Aims.Interplanetary dust particle (IDP) matter probably evolved under irradiation in the interstellar medium (ISM) and the solar nebula. Currently IDPs are exposed to irradiation in the Solar System. Here the effects of UV and proton processing on IDP matter are studied experimentally. The structure and chemical composition of the bulk of carbon matter in IDPs is characterized. Methods: .Several IDPs were further irradiated in the laboratory using ultraviolet (UV) photons and protons in order to study the effects of such processing. By means of infrared and Raman spectroscopy, IDPs were also compared to different materials that serve as analogs of carbon grains in the dense and diffuse ISM. Results: .The carbonaceous fraction of IDPs is dehydrogenated by exposure to hard UV photons or 1 MeV protons. On the other hand, proton irradiation at lower energies (20 keV) leads to an efficient hydrogenation of the carbonaceous IDP matter. The dominant type of carbon in IDPs, observed with Raman and infrared spectroscopy, is found to be either a form of amorphous carbon (a-C) or hydrogenated amorphous carbon (a-C:H), depending on the IDP, consisting of aromatic units with an average domain size of 1.35 nm (5-6 rings in diameter), linked by aliphatic chains. Conclusions: .The D- and 15N-enrichments associated to an aliphatic component in some IDPs are probably the result of chemical reactions at cold temperatures. It is proposed that the amorphous carbon in IDPs was formed by energetic processing (UV photons and cosmic rays) of icy grains, maybe during the dense cloud stage, and more likely on the surface of the disk during the T Tauri phase of our Sun. This would explain the isotopic anomalies and morphology of IDPs. Partial annealing, 300-400°C, is required to convert an organic residue from ice photoprocessing into the amorphous carbon with low heteroatom content found in IDPs. Such annealing might have occurred as the particles approached the Sun and/or during atmospheric entry heating

UV photoprocessing of CO2 ice: a complete quantification of photochemistry and photon-induced desorption processes

Ice mantles that formed on top of dust grains are photoprocessed by the secondary ultraviolet (UV) field in cold and dense molecular clouds. UV photons induce photochemistry and desorption of ice molecules. Experimental simulations dedicated to ice analogs under astrophysically relevant conditions are needed to understand these processes. We present UV-irradiation experiments of a pure CO2 ice analog. Calibration of the QMS allowed us to quantify the photodesorption of molecules to the gas phase. This information was added to the data provided by the FTIR on the solid phase to obtain a complete quantitative study of the UV photoprocessing of an ice analog. Experimental simulations were performed in an ultra-high vacuum chamber. Ice samples were deposited onto an infrared transparent window at 8K and were subsequently irradiated with a microwave-discharged hydrogen flow lamp. After irradiation, ice samples were warmed up until complete sublimation was attained. Photolysis of CO2 molecules initiates a network of photon-induced chemical reactions leading to the formation of CO, CO3 ,O2 , and O3 . During irradiation, photon-induced desorption of CO and, to a lesser extent, O2 and CO2 took place through a process called indirect desorption induced by electronic transitions (DIET), with maximum photodesorption yields (Ypd) of 1.2 x 10-2 molecules/incident photon , 9.3 x 10-4 molecules/incident photon , and 1.1 x 10-4 molecules/incident photon , respectively. Calibration of mass spectrometers allows a direct quantification of photodesorption yields instead of the indirect values that were obtained from infrared spectra in most previous works. Supplementary information provided by infrared spectroscopy leads to a complete quantification, and therefore a better understanding, of the processes taking place in UV-irradiated ice mantles