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

Spectrally-resolved UV photodesorption of CH4 in pure and layered ices

Context. Methane is among the main components of the ice mantles of insterstellar dust grains, where it is at the start of a rich solid-phase chemical network. Quantification of the photon-induced desorption yield of these frozen molecules and understanding of the underlying processes is necessary to accurately model the observations and the chemical evolution of various regions of the interstellar medium. Aims. This study aims at experimentally determining absolute photodesorption yields for the CH4 molecule as a function of photon energy. The influence of the ice composition is also investigated. By studying the methane desorption from layered CH4:CO ice, indirect desorption processes triggered by the excitation of the CO molecules is monitored and quantified. Methods. Tunable monochromatic VUV light from the DESIRS beamline of the SOLEIL synchrotron is used in the 7 - 13.6 eV (177 - 91 nm) range to irradiate pure CH4 or layers of CH4 deposited on top of CO ice samples. The release of species in the gas phase is monitored by quadrupole mass spectrometry and absolute photodesorption yields of intact CH4 are deduced. Results. CH4 photodesorbs for photon energies higher than ~9.1 eV (~136 nm). The photodesorption spectrum follows the absorption spectrum of CH4, which confirms a desorption mechanism mediated by electronic transitions in the ice. When it is deposited on top of CO, CH4 desorbs between 8 and 9 eV with a pattern characteristic of CO absorption, indicating desorption induced by energy transfer from CO molecules. Conclusions. The photodesorption of CH4 from the pure ice in various interstellar environments is around 2.0 x 10^-3 molecules per incident photon. Results on CO-induced indirect desorption of CH4 provide useful insights for the generalization of this process to other molecules co-existing with CO in ice mantles

Using radio astronomical receivers for molecular spectroscopic characterization in astrochemical laboratory simulations: A proof of concept

We present a proof of concept on the coupling of radio astronomical receivers and spectrometers with chemical reactorsand the performances of the resulting setup for spectroscopy and chemical simulations in laboratory astrophysics. Several experiments including cold plasma generation and UV photochemistry were performed in a 40\,cm long gas cell placed in the beam path of the Aries 40\,m radio telescope receivers operating in the 41-49 GHz frequency range interfaced with fast Fourier transform spectrometers providing 2 GHz bandwidth and 38 kHz resolution. The impedance matching of the cell windows has been studied using different materials. The choice of the material and its thickness was critical to obtain a sensitivity identical to that of standard radio astronomical observations. Spectroscopic signals arising from very low partial pressures of CH3OH, CH3CH2OH, HCOOH, OCS,CS, SO2 (<1E-03 mbar) were detected in a few seconds. Fast data acquisition was achieved allowing for kinetic measurements in fragmentation experiments using electron impact or UV irradiation. Time evolution of chemical reactions involving OCS, O2 and CS2 was also observed demonstrating that reactive species, such as CS, can be maintained with high abundance in the gas phase during these experiments.Comment: Accepted for publication in Astronomy and Astrophysics in September 21, 2017. 16 pages, 18 figure

Gas phase Elemental abundances in Molecular cloudS (GEMS) VII. Sulfur elemental abundance

Gas phase Elemental abundances in molecular CloudS (GEMS) is an IRAM 30m large program aimed at determining the elemental abundances of carbon (C), oxygen (O), nitrogen (N), and sulfur (S) in a selected set of prototypical star-forming filaments. In particular, the elemental abundance of S remains uncertain by several orders of magnitude and its determination is one of the most challenging goals of this program. We have carried out an extensive chemical modeling of the fractional abundances of CO, HCO$^+$, HCN, HNC, CS, SO, H$_2$S, OCS, and HCS$^+$ to determine the sulfur depletion toward the 244 positions in the GEMS database. These positions sample visual extinctions from A$_V$ $\sim$ 3 mag to $>$50 mag, molecular hydrogen densities ranging from a few 10$^3$~cm$^{-3}$ to 3$\times$10$^6$~cm$^{-3}$, and T$_k$ $\sim$ 10$-$35 K. Most of the positions in Taurus and Perseus are best fitted assuming early-time chemistry, t=0.1 Myr, $\zeta_{H_2}$$\sim$ (0.5$-$1)$\times$10$^{-16}$ s$^{-1}$, and [S/H]$\sim$1.5$\times$10$^{-6}$. On the contrary, most of the positions in Orion are fitted with t=1~Myr and $\zeta_{H_2}$$\sim$ 10$^{-17}$ s$^{-1}$. Moreover, $\sim$40% of the positions in Orion are best fitted assuming the undepleted sulfur abundance, [S/H]$\sim$1.5$\times$10$^{-5}$. Our results suggest that sulfur depletion depends on the environment. While the abundances of sulfur-bearing species are consistent with undepleted sulfur in Orion, a depletion factor of $\sim$20 is required to explain those observed in Taurus and Perseus. We propose that differences in the grain charge distribution in the envelopes of the studied clouds might explain these variations. The shocks associated with past and ongoing star formation could also contribute to enhance [S/H] in Orion.Comment: 22 pages, 15 figures, Astronomy and Astrophysics, in pres

Methanol ice co-desorption as a mechanism to explain cold methanol in the gas-phase

Context. Methanol is formed via surface reactions on icy dust grains. Methanol is also detected in the gas-phase at temperatures below its thermal desorption temperature and at levels higher than can be explained by pure gas-phase chemistry. The process that controls the transition from solid state to gas-phase methanol in cold environments is not understood. Aims. The goal of this work is to investigate whether thermal CO desorption provides an indirect pathway for methanol to co-desorb at low temperatures. Methods. Mixed CH₃OH:CO/CH₄ ices were heated under ultra-high vacuum conditions and ice contents are traced using RAIRS (reflection absorption IR spectroscopy), while desorbing species were detected mass spectrometrically. An updated gas-grain chemical network was used to test the impact of the results of these experiments. The physical model used is applicable for TW Hya, a protoplanetary disk in which cold gas-phase methanol has recently been detected. Results. Methanol release together with thermal CO desorption is found to be an ineffective process in the experiments, resulting in an upper limit of ≤ 7.3 × 10−7 CH₃OH molecules per CO molecule over all ice mixtures considered. Chemical modelling based on the upper limits shows that co-desorption rates as low as 10−6 CH₃OH molecules per CO molecule are high enough to release substantial amounts of methanol to the gas-phase at and around the location of the CO thermal desorption front in a protoplanetary disk. The impact of thermal co-desorption of CH₃OH with CO as a grain-gas bridge mechanism is compared with that of UV induced photodesorption and chemisorption

Gas phase Elemental abundances in Molecular cloudS (GEMS) : IV. Observational results and statistical trends

Gas phase Elemental abundances in Molecular CloudS (GEMS) is an IRAM 30 m Large Program designed to provide estimates of the S, C, N, and O depletions and gas ionization degree, X(e(-)), in a selected set of star-forming filaments of Taurus, Perseus, and Orion. Our immediate goal is to build up a complete and large database of molecular abundances that can serve as an observational basis for estimating X(e(-)) and the C, O, N, and S depletions through chemical modeling. We observed and derived the abundances of 14 species ((CO)-C-13, (CO)-O-18, HCO+, (HCO+)-C-13, (HCO+)-O-18, HCN, (HCN)-C-13, HNC, HCS+, CS, SO, (SO)-S-34, H2S, and OCS) in 244 positions, covering the A(V) similar to 3 to similar to 100 mag, n(H-2) similar to a few 10(3) to 10(6) cm(-3), and T-k similar to 10 to similar to 30 K ranges in these clouds, and avoiding protostars, HII regions, and bipolar outflows. A statistical analysis is carried out in order to identify general trends between different species and with physical parameters. Relations between molecules reveal strong linear correlations which define three different families of species: (1) (CO)-C-13 and (CO)-O-18 isotopologs; (2) (HCO+)-C-13, (HCO+)-O-18, H-13 CN, and HNC; and (3) the S-bearing molecules. The abundances of the CO isotopologs increase with the gas kinetic temperature until T-K similar to 15 K. For higher temperatures, the abundance remains constant with a scatter of a factor of similar to 3. The abundances of H-13 CO+, HC18 O+, H-13 CN, and HNC are well correlated with each other, and all of them decrease with molecular hydrogen density, following the law proportional to n(H-2)(-0.8 +/- 0.2). The abundances of S-bearing species also decrease with molecular hydrogen density at a rate of (S-bearing/H)(gas) proportional to n(H-2)(-0.6 +/- 0.1). The abundances of molecules belonging to groups 2 and 3 do not present any clear trend with gas temperature. At scales of molecular clouds, the (CO)-O-18 abundance is the quantity that better correlates with the cloud mass. We discuss the utility of the (CO)-C-13/(CO)-O-18, HCO+/(HCO+)-C-13, and H-13 CO+/(HCN)-C-13 abundance ratios as chemical diagnostics of star formation in external galaxies.Peer reviewe

Broad-band high-resolution rotational spectroscopy for laboratory astrophysics

We present a new experimental set-up devoted to the study of gas phase molecules and processes using broad-band high spectral resolution rotational spectroscopy. A reactor chamber is equipped with radio receivers similar to those used by radio astronomers to search for molecular emission in space. The whole range of the Q (31.5-50 GHz) and W bands (72-116.5 GHz) is available for rotational spectroscopy observations. The receivers are equipped with 16 × 2.5 GHz fast Fourier transform spectrometers with a spectral resolution of 38.14 kHz allowing the simultaneous observation of the complete Q band and one-third of the W band. The whole W band can be observed in three settings in which the Q band is always observed. Species such as CH3CN, OCS, and SO2 are detected, together with many of their isotopologues and vibrationally excited states, in very short observing times. The system permits automatic overnight observations, and integration times as long as 2.4 × 105 s have been reached. The chamber is equipped with a radiofrequency source to produce cold plasmas, and with four ultraviolet lamps to study photochemical processes. Plasmas of CH4, N2, CH3CN, NH3, O2, and H2, among other species, have been generated and the molecular products easily identified by the rotational spectrum, and via mass spectrometry and optical spectroscopy. Finally, the rotational spectrum of the lowest energy conformer of CH3CH2NHCHO (N-ethylformamide), a molecule previously characterized in microwave rotational spectroscopy, has been measured up to 116.5 GHz, allowing the accurate determination of its rotational and distortion constants and its search in space.We thank the European Research Council for funding support under Synergy Grant ERC-2013-SyG, G.A. 610256 (NANOCOSMOS). IT, VJH, and JLD acknowledge additional partial support from the Spanish State Research Agency (AEI) through grant FIS2016-77726-C3-1-P. JAMG, LM, and GS acknowledge additional partial support from the Spanish State Research Agency (AEI) through grant MAT2017-85089-C2-1R. We thank David López Romero for his help during the process of installation, commissioning, and cleaning of the chamber. We would like to thank Kremena Makasheva for the useful comments and suggestions during the experiments with Hexamethyldisiloxane. We would also like to thank Rosa Lebrón, Jesús Quintanilla, and Cristina Soria for providing us with the sample of N-ethylformamide. Sandra I. Ramírez acknowledges support from the FONCICYT under grant number 291842. Celina Bermúdez thanks the Spanish Ministerio de Ciencia Innovación y Universidades for the Juan de la Cierva grant FJCI-2016-27983