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13 pags., 5 figs., 5 tabs., The recent detection of urea in the interstellar medium raises questions about its stability in different astronomical environments. In this work, we have studied the stability of urea ices and urea/water ice mixtures under vacuum-ultraviolet (VUV; 6.3–10.9 eV) irradiation and high-energy (5 keV) electron bombardment at 30, 100, and 200 K. The evolution of the ices was monitored with infrared spectroscopy. CO2, HNCO, and OCN− were identified as reaction products in the 30 K samples. At the higher temperatures CO2 and HNCO were hardly found in the processed ices. The measurements provided destruction cross-sections and allowed the derivation of radiation yields, G100, and half-life doses for urea. G100 values were found to be low (≈3.6–0.3 molecules/100 eV) both for VUV photons and high-energy electrons with electrons being slightly more efficient for the destruction of the molecule. These low G100 values are likely due to favourable mechanisms of energy dissipation or urea recombination. The stability of urea under irradiation increases with temperature which suggests that higher mobility improves the repair mechanisms. Estimates based on these laboratory data indicate that urea should be stable (≈108–109 yr) against irradiation in cold dense clouds and hot cores. It would not survive long (≈103–104 yr) on the bare surface of a Kuiper belt object, but would be well protected (≈109 yr) against radiation below a 30 μm ice layer. The high resistance of the molecule to radiation damage makes it a good candidate for prebiotic chemistry., BM, IT, and VJH acknowledge support from the Ministerio de Economia y Competitividad (MINECO) and the Ministerio de Ciencia e Innovacion´ (MICINN) of Spain under grants FIS2016-77726-C3-1-P and PID2020-113084GB-100 and from the European Union under grant ERC-2013-Syg-210656-NANOCOSMOS. GMMC and HC are grateful for funding from MICINN under grant PID2020-118974GB-C21, and PhD fellowship FPU-17/03172. IJ-S acknowledges financial support from grant No PID2019-105552RBC41 by the Spanish Ministry of Science and Innovation/State Agency of Research MCIN/AEI/10.13039/501100011033. GMMC, HC, and IJ-S also acknowledge support from MDM-2017–0737 Unidad de Excelencia ‘Maria de Maeztu’ – CAB (CSIC-INTA). The i-LINK program (grant LINKA 20353) from CSIC is also acknowledged.

9 pags., 6 figs., Evolved stars are foundries of chemical complexity, gas and dust that provide the building blocks of planets and life, and dust nucleation first occurs in their photosphere. The circumstellar regions enveloping these stars, despite their importance, remain hidden to many observations, and dust formation processes are therefore still poorly understood. Laboratory astrophysics provides complementary routes to unveil these chemical processes, but most experiments rely on combustion or plasma decomposition of molecular precursors under physical conditions far removed from those in space. To reproduce and characterize the bottom-up dust formation process, we have built an ultra-high vacuum machine combining atomic gas aggregation with advanced in situ characterization techniques. We show that carbonaceous dust analogues that formed from low-pressure gas-phase condensation of carbon atoms in a hydrogen atmosphere, in a ratio of carbon to molecular hydrogen similar to that reported for evolved stars, lead to the formation of amorphous carbon nanograins and aliphatic carbon clusters. Aromatic species and fullerenes do not form effectively under these conditions, raising implications for a revision of the chemical mechanisms taking place in circumstellar envelopes., We thank the European Research Council for funding support under Synergy Grant ERC-2013-SyG, G.A. 610256 (NANOCOSMOS). We also acknowledge partial support from the Spanish Research Agency (AEI) through grants MAT2017-85089-c2-1R, FIS2016-77578-R and FIS2016-77726-C3-1-P. Support from the FotoArt-CM Project (P2018/NMT-4367) through the Program of R&D activities between research groups in Technologies 2013, cofinanced by European Structural Funds, is also recognized.

16 pags., 11 figs., 2 tabs., The first stages of polymerization in plasmas of Ar/CH have been studied both experimentally and using a kinetic model, by following the time evolution of the main neutral and ionic species in the discharge. The abundances of the different neutrals and ions have been measured by quadrupole mass spectrometry in conditions specifically chosen to avoid dust formation in the plasma. Maxima occurring at different times from the ignition of the discharge were detected for the density of the neutral species sampled, generally consistent with a stepwise polymerization mechanism. Ions were found to fundamentally follow the trend of their neutral counterparts, with the time evolution for negative ions stressing the difference in the chemical mechanisms responsible for the formation of the two primitive anions, CH and HCC. Positive and negative ion distributions were measured in the steady state of the discharge. Detection of anions with up to 22 carbon atoms was possible in mixtures with high acetylene content. A volume averaged kinetic model with a simple description of the Ar/CH chemistry was used to identify the main reaction pathways and was able to satisfactory reproduce the experimental results., This work has been funded by the Ministerio de Economía y Competitividad (MINECO) and the Ministerio de Ciencia e Innovacion of Spain under Grants FIS2016-77726-C3.1.P and PID2020-113084GB-100 respectively and by the European Union under Grant ERC-2013-Syg-210656-NANOCOSMOS

16 pags., 9 figs., 9 tabs. -- Unified Astronomy Thesaurus concepts: Pre-biotic astrochemistry (2079); Astrochemistry (75); Ice destruction (2091); Molecular physics (2058); Molecule destruction (2075); Spectral line identification (2073); Laboratory astrophysics (2004); Theoretical models (2107); Experimental techniques (2078), 2-aminooxazole (2AO), a N-heterocyclic molecule, has been proposed as an intermediate in prebiotic syntheses. It has been demonstrated that it can be synthesized from small molecules such as cyanamide and glycoaldehyde, which are present in interstellar space. The aim of this work is to provide infrared (IR) spectra, in the solid phase for conditions typical of astrophysical environments and to estimate its stability toward UV photons and cosmic rays. IR (4000-600 cm-1) absorption spectra at 20 K, 180 K, and 300 K, IR band strengths, and room-temperature UV (120-250 nm) absorption spectra are given for the first time for this species. Destruction cross sections of ≈9.5 10-18 cm2 and ≈2 10-16 cm2 were found in the irradiation at 20 K of pure 2AO and 2AO:H2O ices with UV (6.3-10.9 eV) photons or 5 keV electrons, respectively. These data were used to estimate half-life times for the molecule in different environments. It is estimated that 2AO could survive UV radiation and cosmic rays in the ice mantles of dense clouds beyond cloud collapse. In contrast, it would be very unstable on the surface of cold solar system bodies like Kuiper Belt objects, but the molecule could still survive within dust grain agglomerates or cometesimals., B.M., V.T., I.T., and V.J.H. are grateful to the Ministerio de Economia y Competitividad (MINECO) of Spain under grant FIS2016-77726-C3-1-P. G.M.M.C., H.C., and C.G.D. acknowledge MINECO support under grant AYA2017–85322-R (AEI/ FEDER, UE), Ph.D. fellowship FPU-17/03172, and MDM2017–0737 Unidad de Excelencia “María de Maeztu”—CAB (CSIC-INTA). I.J.S. acknowledges partial support from the Spanish FEDER (ESP2017-86582-C4-1-R) and the State Research Agency (PID2019-105552RB-C41).

IOP Publishing [Society Publisher] Silicon is present in interstellar dust grains, meteorites and asteroids, and to date 13 silicon-bearing molecules have been detected in the gas phase toward late-type stars or molecular clouds, including silane and silane derivatives. In this work, we have experimentally studied the interaction between atomic silicon and hydrogen under physical conditions mimicking those in the atmosphere of evolved stars. We have found that the chemistry of Si, H, and H2 efficiently produces silane (SiH4), disilane (Si2H6) and amorphous hydrogenated silicon (a-Si:H) grains. Silane has been definitely detected toward the carbon-rich star IRC +10216, while disilane has not been detected in space yet. Thus, based on our results, we propose that gas-phase reactions of atomic Si with H and H2 are a plausible source of silane in C-rich asymptotic giant branch stars, although its contribution to the total SiH4 abundance may be low in comparison with the suggested formation route by catalytic reactions on the surface of dust grains. In addition, the produced a-Si:H dust analogs decompose into SiH4 and Si2H6 at temperatures above 500 K, suggesting an additional mechanism of formation of these species in envelopes around evolved stars. We have also found that the exposure of these dust analogs to water vapor leads to the incorporation of oxygen into Si–O–Si and Si–OH groups at the expense of SiH moieties, which implies that if this kind of grain is present in the interstellar medium, it will probably be processed into silicates through the interaction with water ices covering the surface of dust grains. We thank the European Research Council for funding support under Synergy grant ERC-2013-SyG, G.A. 610256 (NANOCOSMOS). Also, we acknowledge partial support from the Spanish MINECO through grants MAT2017-85089-c2-1R, FIS2016-77726-C3-1-P, FIS2016-77578-R, AYA2016-75066-C2-1-P and RyC-2014-16277. Support from the FotoArt-CM Project (P2018/NMT 4367) through the Program of R&D activities between research groups in Technologies 2013, cofinanced by European Structural Funds, is also acknowledged. G.T.C. acknowledges funding from the Comunidad Autonoma de Madrid (PEJD-2018-PRE/IND-9029). Peerreview

8 pags., 9 figs., 4 tabs., Urea is a molecule of great interest in chemistry and biology. In particular, it is considered a key building block in prebiotic chemistry on Earth. The hypothesis of its possible exogenous origin has been reinforced after the recent detection of this molecule in the interstellar medium, where it is believed to form in the ice mantles of dust grains. In this work the infrared spectra of urea ices and urea:HO ice mixtures have been studied both experimentally and theoretically. Urea ices were generated by vapour deposition at temperatures between 10 K and 270 K. It was found that an amorphous phase is formed at temperatures below 200 K. A theoretical modelling of crystalline urea and of a tentative amorphous urea solid phase, as well as of amorphous urea:HO ice mixtures, has been performed. The corresponding infrared spectra were simulated with density functional theory. The main spectral features observed in the various solid samples are interpreted with the help of the theoretical results. Infrared band strengths are also provided for amorphous and crystalline urea. The infrared spectroscopic information given in this work is expected to be useful for the detection and quantification of urea in astrophysical ices., This work was funded by the Ministerio de Economia y Competitividad (MINECO) and the Ministerio de Ciencia e Innovacion (MCI) of Spain under grants FIS2016-77726-C3-1-P and PID2020-113084GB-I00, respectively, and by the European Union under grant ERC-2013-Syg-210656-NANOCOSMOS. The computation time provided by the Centro Tecnico de Informatica, cluster Trueno from CSIC and Centro de Supercomputacio´n de Galicia CESGA is deeply acknowledged.

Interstellar carbonaceous dust is mainly formed in the innermost regions of circumstellar envelopes around carbon-rich asymptotic giant branch (AGB) stars. In these highly chemically stratified regions, atomic and diatomic carbon, along with acetylene are the most abundant species after H(2) and CO. In a previous study, we addressed the chemistry of carbon (C and C(2)) with H(2) showing that acetylene and aliphatic species form efficiently in the dust formation region of carbon-rich AGBs whereas aromatics do not. Still, acetylene is known to be a key ingredient in the formation of linear polyacetylenic chains, benzene and polycyclic aromatic hydrocarbons (PAHs), as shown by previous experiments. However, these experiments have not considered the chemistry of carbon (C and C(2)) with C(2)H(2). In this work, by employing a sufficient amount of acetylene, we investigate its gas-phase interaction with atomic and diatomic carbon. We show that the chemistry involved produces linear polyacetylenic chains, benzene and other PAHs, which are observed with high abundances in the early evolutionary phase of planetary nebulae. More importantly, we have found a non-negligible amount of pure and hydrogenated carbon clusters as well as aromatics with aliphatic substitutions, both being a direct consequence of the addition of atomic carbon. The incorporation of alkyl substituents into aromatics can be rationalized by a mechanism involving hydrogen abstraction followed by methyl addition. All the species detected in gas phase are incorporated into the nanometric sized dust analogues, which consist of a complex mixture of sp, sp(2) and sp(3) hydrocarbons with amorphous morphology.

2 págs., 1 fig. -- Proceedings IAU Symposium 2019, The desorption of volatile molecules from dust grains in cold dense clouds is crucial for the chemical inventory in the various stages of cloud collapse. In this work we investigate the desorption of N2, CO, CH4 and CO2 from surfaces of hydrogenated amorphous carbon (HAC), which, according to IR observations, is one of the main components of interstellar dust., This work was funded by the EU, ERC-2013-Syg-210656-NANOCOSMOS and by the MINECO of Spain, Grant FIS 2016-77726-C3-1-P.

8 pags., 5 figs., 5 tabs., 1 app., Context. Dinitriles with a saturated hydrocarbon skeleton and a −C≡N group at each end can have large electric dipole moments. Their formation can be related to highly reactive radicals such as CH2CN, C2N, or CN. Thus, these saturated dinitriles are potential candidates to be observed in the interstellar medium (ISM). Aims. Our goal is the investigation of the rotational spectrum of one of the simplest dinitriles N≡C−CH2−CH2−C≡N, succinonitrile, whose actual rotational parameters are not precise enough to allow its detection in the ISM. In addition, the rotational spectra for its vibrational excited states will be analysed. Methods. The rotational spectra of succinonitrile was measured in the frequency range 72−116.5 GHz using a new broadband millimeter-wave spectrometer based on radio astronomy receivers with Fast Fourier Transform backends. The identification of the vibrational excited states of succinonitrile was supported by high-level ab initio calculations on the harmonic and anharmonic force fields. Results. A total of 459 rotational transitions with maximum values of J and Ka quantum numbers 70 and 14, respectively, were measured for the ground vibrational state of succinonitrile. The analysis allowed us to accurately determine the rotational, quartic, and sextic centrifugal distortion constants. Up to eleven vibrational excited states, resulting from the four lowest frequency vibrational modes ν13, ν12, ν24, and ν23 were identified. In addition to the four fundamental modes, we observed overtones together with some combination states. The rotational parameters for the ground state were employed to unsuccessfully search for succinonitrile in the cold and warm molecular clouds Orion KL, Sgr B2(N), B1-b, and TMC-1, using the spectral surveys captured by IRAM 30 m at 3 mm and the Yebes 40 m at 1.3 cm and 7 mm., We thank the European Research Council for funding support under Synergy Grant ERC-2013-SyG, G.A. 610256 (NANOCOSMOS). CB would like to thank the Ministerio de Ciencia, Innovación y Universidades for a Juan de la Cierva postdoctoral fellowship (FJCI-2016-27983). IT, VJH, and JLD acknowledge additional partial support from the Spanish State Research Agency (AEI) through grant FIS2016-77726-C3-1-P. This work was also based on observations carried out with the IRAM 30-meter telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain).

13 pags., 7 figs., 1 tab.-- Published as part of The Journal of Physical Chemistry virtual special issue “F. Javier Aoiz Festschrift”., The ionic polymerization of acetylene in cold plasmas of C2H2/He and C2H2/Ar has been experimentally studied and modeled in radio frequency (rf) discharges with conditions selected to avoid particle formation. Steady-state distributions of positive and negative ions were measured with mass spectrometry. All the measured distributions are dominated by ions with an even number of carbon atoms, reflecting the characteristic polyyne structures typical for the polymerization of acetylene. The distributions show a monotonic decrease in intensity from ions with two carbon atoms until the highest number of atoms detected. For cations, the distributions extend until 12 carbon atoms. The anion distributions extend further, and negative ions with 20 C atoms are observed in the C2H2/Ar plasma. From the measured mass spectra it is not possible to decide on the possible presence of aromatic species in ions with more than six carbon atoms. A simple model assuming a homogeneous discharge was used to describe the plasma kinetics and could account for the measured ion distributions with reasonable values of charge density and electron temperature. The results of this work stress the important role of the vinylidene anion and indicate that Ar and He do not have much influence on the carbon chemistry., Funding from EU project ERC-2013-Syg-610256 NANOCOSMOS and from the MINECO of Spain under grant FIS2016-77726-C3-1P is gratefully acknowledged.

74th ISMS 2019, University of Illinois, at Urbana-Champaign, June 17 - 21, 2019

25th International Conference on High Resolution Molecular Spectroscopy. 3 al 7 de septiembre en el Bizkaia Aretoa (Bilbao, Spain)(2018). --.http://www.hrms-bilbao2018.com/

13 pags., 12 figs., 2 tabs., Interstellar carbonaceous dust is mainly formed in the innermost regions of circumstellar envelopes around carbon-rich asymptotic giant branch stars (AGBs). In these highly chemically stratified regions, atomic and diatomic carbon, along with acetylene, are the most abundant species after H and CO. In a previous study, we addressed the chemistry of carbon (C and C) with H showing that acetylene and aliphatic species form efficiently in the dust formation region of carbon-rich AGBs whereas aromatics do not. Still, acetylene is known to be a key ingredient in the formation of linear polyacetylenic chains, benzene, and polycyclic aromatic hydrocarbons (PAHs), as shown by previous experiments. However, these experiments have not considered the chemistry of carbon (C and C) with CH. In this work, by employing a sufficient amount of acetylene, we investigate its gas-phase interaction with atomic and diatomic carbon. We show that the chemistry involved produces linear polyacetylenic chains, benzene, and other PAHs, which are observed with high abundances in the early evolutionary phase of planetary nebulae. More importantly, we have found a nonnegligible amount of pure and hydrogenated carbon clusters as well as aromatics with aliphatic substitutions, both being a direct consequence of the addition of atomic carbon. The incorporation of alkyl substituents into aromatics can be rationalized by a mechanism involving hydrogen abstraction followed by methyl addition. All the species detected in the gas phase are incorporated into nanometric-sized dust analogs, which consist of a complex mixture of sp, sp, and sp hydrocarbons with amorphous morphology., We thank the European Research Council for funding support under Synergy grant ERC-2013-SyG, G.A. 610256 (NANOCOSMOS). Also, partial support from the Spanish Research Agency (AEI) through grants MAT2017-85089-c2- 1R, FIS2016-77578-R, FIS2016-77726-C3-1-P, AYA2016- 75066-C2-1-P, and RyC-2014-16277 is acknowledged. Support from the FotoArt-CM Project (P2018/NMT 4367) through the Program of R&D activities between research groups in Technologies 2013, co-financed by European Structural Funds, is also acknowledged. G.TC. acknowledges funding from the Comunidad Autónoma de Madrid (PEJD-2018-PRE/ IND-9029)

Champaign-Urbana, Illinois, United States, 17 - 21 June 2019

12 pags., 8 figs., 3 tabs., The interaction of volatile species with carbonaceous interstellar dust analogues is of relevance in the chemistry and physics of dense clouds in the interstellar medium. Two deposits of hydrogenated amorphous carbon (HAC), with different morphologies and aromatic versus aliphatic ratio in their structure, have been grown to model interstellar dust. The interaction of N2, CO, CH4, and CO2 with these two surfaces has been investigated using thermal programmed desorption (TPD). Desorption energy distributions were obtained by analysing TPD spectra for one monolayer coverage with the Polanyi–Wigner equation. The desorption energies found in this work for N2, CO, and CH4 are larger by 10–20 per cent than those reported in the literature for siliceous or amorphous solid water surfaces. Moreover, the experiments suggest that the interaction of the volatiles with the aromatic substructure of HAC is stronger than that with the aliphatic part. Desorption of CO2 from the HAC surfaces follows zero-order kinetics, reflecting the predominance of CO2–CO2 interactions. A model simulation of the heating of cold cloud cores shows that the volatiles considered in this work would desorb sequentially from carbonaceous dust surfaces with desorption times ranging from hundreds to tens of thousands of years, depending on the molecule and on the mass of the core, This work was funded by the Ministerio de Economia y Competitividad (MINECO) of Spain under grant FIS2016-77726-C3-1-P and by the European Union under grant ERC-2013-Syg-210656- NANOCOSMOS

13 pags., 8 figs. -- Open Access funded by Creative Commons Atribution Licence 4.0, The increasing demand for nanostructured materials is mainly motivated by their key role in a wide variety of technologically relevant fields such as biomedicine, green sustainable energy or catalysis. We have succeeded to scale-up a type of gas aggregation source, called a multiple ion cluster source, for the generation of complex, ultra-pure nanoparticles made of different materials. The high production rates achieved (tens of g/day) for this kind of gas aggregation sources, and the inherent ability to control the structure of the nanoparticles in a controlled environment, make this equipment appealing for industrial purposes, a highly coveted aspect since the introduction of this type of sources. Furthermore, our innovative UHV experimental station also includes in-flight manipulation and processing capabilities by annealing, acceleration, or interaction with background gases along with in-situ characterization of the clusters and nanoparticles fabricated. As an example to demonstrate some of the capabilities of this new equipment, herein we present the fabrication of copper nanoparticles and their processing, including the controlled oxidation (from Cu to CuO through CuO, and their mixtures) at different stages in the machine., This work was supported by the European Union [grant number ERC-2013-SyG 610256 NANOCOSMOS]; the Spanish MINECO [grant numbers MAT2017-85089-C2-1-R, MAT2014-54231-C4-1-P, MAT2014-54231- C4-4-P, MAT2014-59772-C2-2-P, FIS2016-77578-R, FIS2013-48087-C2-1P, FIS2016-77726-C3-1P and CSIC13-4E-1775].

10 pags., 9 figs., 2 tabs., Interstellar (IS) dust analogs, based on amorphous hydrogenated carbon (a-C:H) were generated by plasma deposition in radio frequency discharges of CH4 + He mixtures. The a-C:H samples were characterized by means of secondary electron microscopy, infrared (IR) spectroscopy and UV-visible reflectivity. DFT calculations of structure and IR spectra were also carried out. From the experimental data, atomic compositions were estimated. Both IR and reflectivity measurements led to similar high proportions (≈50%) of H atoms, but there was a significant discrepancy in the sp2/sp3 hybridization ratios of C atoms (sp2/sp3 = 1.5 from IR and 0.25 from reflectivity). Energetic processing of the samples with 5 keV electrons led to a decay of IR aliphatic bands and to a growth of aromatic bands, which is consistent with a dehydrogenation and graphitization of the samples. The decay of the CH aliphatic stretching band at 3.4 μm upon electron irradiation is relatively slow. Estimates based on the absorbed energy and on models of cosmic ray (CR) flux indicate that CR bombardment is not enough to justify the observed disappearance of this band in dense IS clouds., This work was funded by the Spanish MINECO under grants FIS2013-48087-C2-1P and FIS2016-77726-C3-1P. European Union funding under the project ERC-2013-Syg 610256 (NANOCOSMOS) is also acknowledged.

I. Tanarro et al. -- 16 pags., 18 figs., app., We present a proof of concept on the coupling of radio astronomical receivers and spectrometers with chemical reactors and 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 di erent 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 (, The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC-SyG-2013 Grant Agreement No. 610256 NANOCOSMOS and from spanish MINECO CSD2009-00038 (ASTROMOL) under the Consolider-Ingenio Program. We also thank spanish MINECO for funding under grants AYA2012-32032, AYA2016-75066-C2-1-P, FIS2013-48087-C2-1-P, FIS2016-77726-C3-1-P, FIS2016-77578-R, MAT2014- 54231-C4-1-P.

International Symposium on Molecular Spectroscopy. 73rd Meeting - June 18-22, 2018 - Champaign-Urbana, Illinois (USA). .--http://isms.illinois.edu / http://hdl.handle.net/2142/100503

Carbonaceous grains make a large part of cosmic dust and contain a significant fraction of the carbon available in the interstellar medium (ISM). Observational evidence for the presence of carbonaceous grains comes mostly from IR absorption spectra. The most intense IR absorption is the 3.4 μm band which is ubiquitous in the diffuse ISM and is also present in other galaxies. It is attributed to CH stretching vibrations of CH2 and CH3 groups; weaker absorptions at 6.85 and 7.27 μm are due to aliphatic bendings, and a broad, weak absorption between 6 and 6.4 μm is assigned to C=C stretching. These observations, together with laboratory work on dust analogs, point to amorphous hydrogenated carbon (abbreviated a-C:H or HAC), as the most likely carrier of these IR bands, and thus as the predominant component of carbonaceous grains; however, the H/C ratio and the proportion of sp2 and sp3 carbon atoms are presently debated. Emission IR bands at 3.3, 6.2, 7.7, 8.6 and 11.2 μm are also seen at many places in the ISM. They have been associated with stretching and bending vibrations of aromatic material and are often referred to as aromatic IR bands (AIB). They are mostly attributed to polycyclic aromatic hydrocarbons (PAHs). Refinements to the original PAH hypothesis including the presence of heteroatoms, aliphatic chains or non-planar defective π domains have been introduced to account for the presence of aliphatic emissions and for the observed band shapes. It is conjectured that the PAHs or PAHs-related molecules responsible for the IR emissions are related with the a-C:H structures responsible for dust absorption either as formation precursors or as destruction products. IR spectroscopy provides also clues on grain evolution. It is generally assumed that carbonaceous grains are formed as nanoparticles in the outflows of carbon-rich AGB stars and evolve from this point. When they reach the diffuse ISM, the grains are subjected to H atom bombardment, which leads to the formation of aliphatic structures, and to UV photon and cosmic ray irradiation that destroy aliphatic structures and lead to graphitization. A core/mantel structure is often assumed for the grains in the diffuse ISM, but models differ on whether the aliphatic chains responsible for the 3.4 μm band are located in the core or in the mantle and present day observations cannot decide on that point. In dense clouds the 3.4 μm band disappears. It is believed that the aliphatic carriers of this band are destroyed somewhere in the transition from the diffuse to the dense ISM, since in the interior of dense clouds UV and cosmic ray fluxes are too weak.

Methyl isocyanate (CH3NCO) was recently found in hot cores and suggested to exist on comet 67P/CG. The incorporation of this molecule into astrochemical networks requires data on its formation and destruction. In this work, ices of pure CH3NCO and of CH3NCO(4%–5%)/H2O mixtures deposited at 20 K were irradiated with a UV D2 lamp (120–400 nm) and bombarded by 5 keV electrons to mimic the secondary electrons produced by cosmic rays (CRs). The destruction of CH3NCO was studied using IR spectroscopy. After processing, the νa–NCO band of CH3NCO disappeared and IR bands corresponding to CO, CO2, OCN−, and HCN/CN− appeared instead. The products of photon and electron processing were very similar. Destruction cross sections and half-life doses were derived from the measurements. Water ice provides a good shield against UV irradiation (half-life dose of ∼64 eV molecule−1 for CH3NCO in water ice), but is not so good against high-energy electrons (half-life dose ∼18 eV molecule−1). It was also found that CH3NCO does not react with H2O over the temperature range 20–200 K. These results indicate that hypothetical CH3NCO in the ices of dense clouds should be stable against UV photons and relatively stable against CRs over the lifetime of a cloud (∼107 yr), and could sublime in the hot core phase. On the surface of a Kuiper Belt object (the original location of comet 67P/CG) the molecule would be swiftly destroyed, by both photons and CRs, but embedded below just 10 μm of water ice, the molecule could survive for ∼109 yr., This work has been funded by the Spanish MINECO under grants FIS2013-48087-C2-1P, FIS2016-C3-1P, and AYA2016- 75066-C2-1-P. J.-C.G. and J.C. also thank the ANR-13-BS05- 0008 IMOLABS and J.-C.G. thanks the Program PCMI (INSU-CNRS) and the Centre National d’Etudes Spatiales (CNES) for funding support. European Union funding under grant ERC-2013-Syg 610256 (NANOCOSMOS) is also acknowledged.

11 págs.; 5 figs.; 6 tabs., A theoretical model of hydrogenated amorphous carbon (HAC) is developed and applied to study the interaction of glycine with HAC surfaces at astronomical temperatures. Two models with different H content are tried for the HAC surface. The theory is applied at the Density Functional Theory (DFT) level, including a semiempirical dispersion correlation potential, d-DFT or Grimme DFT-D2. The level of theory is tested on glycine adsorption on a Si(001) surface. Crystalline glycine is also studied in its two stable phases, a and b, and the metastable g phase. For the adsorption on Si or HAC surfaces, molecular glycine is introduced in the neutral and zwitterionic forms, and the most stable configurations are searched. All theoretical predictions are checked against experimental observations. HAC films are prepared by plasma enhanced vapor deposition at room temperature. Glycine is deposited at 20 K into a high vacuum, cold temperature chamber, to simulate astronomical conditions. Adsorption takes place through the acidic group COO and when several glycine molecules are present, they form H-bond chains among them. Comparison between experiments and predictions suggests that a possible way to improve the theoretical model would require the introduction of aliphatic chains or a polycyclic aromatic core. The lack of previous models to study the interaction of amino-acids with HAC surfaces provides a motivation for this work. © the Owner Societies 2015, This research has been carried out with funding from Spanish MINECO, Projects FIS2013-48087-C2-1-P and CDS2009-00038, and EU project ERC-2013-Syg 610256. O. G. acknowledges Ramón y Cajal Program and project CGL2013-48415-C2-1-R. Some calculations were performed at CESGA and TRUENO.

9 pags., 5 figs., 6 tabs., Methyl isocyanate has been recently detected in comet 67P/Churyumov–Gerasimenko (67P/CG) and in the interstellar medium. New physicochemical studies on this species are now necessary as tools for subsequent studies in astrophysics. In this work, infrared spectra of solid CH3NCO have been obtained at temperatures of relevance for astronomical environments. The spectra are dominated by a strong, characteristic multiplet feature at 2350–2250 cm−1, which can be attributed to the asymmetric stretching of the NCO group. A phase transition from amorphous to crystalline methyl isocyanate is observed at ∼90 K. The band strengths for the absorptions of CH3NCO in ice at 20 K have been measured. Deuterated methyl isocyanate is used to help with the spectral assignment. No X-ray structure has been reported for crystalline CH3NCO. Here we advance a tentative theoretical structure, based on density functional theory (DFT) calculations, derived taking the crystal of isocyanic acid as a starting point. A harmonic theoretical spectrum is then calculated for the proposed structure and compared with the experimental data. A mixed ice of H2O and CH3NCO was formed by simultaneous deposition of water and methyl isocyanate at 20 K. The absence of new spectral features indicates that methyl isocyanate and water do not react appreciably at 20 K, but form a stable mixture. The high CH3NCO/H2O ratio reported for comet 67P/CG, and the characteristic structure of the 2350–2250 cm−1 band, makes it a very good candidate for future astronomical searches., This work was funded by the European Union under grant ERC-2013-Syg 610256 (NANOCOSMOS) and by the Spanish MINECO CSD2009-00038 (ASTROMOL) within the Consolider–Ingenio Program. MINECO funding from grants FIS2013-48087-C2-1P, FIS2016-C3-1P, AYA2012- 32032 and AYA2016-75066-C2-1-P is also acknowledged. G. M. acknowledges MINECO PhD grant BES-2014-0693. JCG and JC also thank the ANR-13-BS05-0008 IMOLABS and JCG thanks the Program PCMI (INSU-CNRS) and the Centre National d’Etudes Spatiales (CNES) for funding support

9 págs.; 8 figs.; 3 tabs., Physical and spectroscopic properties of ices of C2H4 and CH4:C2H4 mixtures with 3:1, 1:1 and 1:3 ratios have been investigated at 30 K. Two laboratories are involved in this work. In one of them, the density and refractive index of the samples have been measured by using a cryogenic quartz microbalance and laser interferometric techniques. In the other one, IR spectra have been recorded in the near- and mid-infrared regions, and band shifts with respect to the pure species, band strengths of the main bands, and the optical constants in both regions have been determined. Previous data on ethylene and the mixtures studied here were scarce. For methane, both the wavenumbers and band strengths have been found to follow a regular pattern of decrease with increasing dilution, but no pattern has been detected for ethylene vibrations. The method employed for the preparation of the samples, by vapour deposition under vacuum, is thought to be adequate to mimic the structure of astrophysical ices. Possible astrophysical implications, especially by means of the optical constants reported here, have been discussed. 2016 The Authors; Published by Oxford University Press on behalf of the Royal Astronomical Society, This work has been funded by the Ministerio de Ciencia y Competitividad (MINECO) of Spain under grants FIS2013-48087-C2-1P, FIS2013-48087-C2-2P and AYA2015-71975-REDT ‘Polvo Cosmico’ by the Ministerio de Ciencia e Innovacion of Spain under grant CDS2009-00038 and by the European Research Council project ERC-2013-Syg 610256 ‘Nanocosmos’. GM acknowledges MINECO PhD grant BES-2014-069355.

[1] We have studied laboratory low pressure (0.1 mbar ≤ p ≤2 mbar) glow air discharges by optical emission spectroscopy to discuss several spectroscopic techniques that could be implemented by field spectrographs, depending on the available spectral resolution, to experimentally quantify the gas temperature associated to transient luminous events (TLEs) occurring at different altitudes including blue jets, giant blue jets, and sprites. Laboratory air plasmas have been analyzed from the near UV (300 nm) to the near IR (1060 nm) with high (up to 0.01 nm) and low (2 nm) spectral resolution commercial grating spectrographs and by an in-house intensified CCD grating spectrograph that we have recently developed for TLE spectral diagnostic surveys with ≃0.45 nm spectral resolution. We discuss the results of lab tests and comment on the convenience of using one or another technique for rotational (gas) temperature determination depending on the altitude and available spectral resolution. Moreover, we compare available low resolution (3 nm ≤Δλ≤7 nm) N2 1PG field recorded sprite spectra at 53 km (≃1 mbar), and resulting vibrational distribution function, with 1 mbar laboratory glow discharge spectrum (Δλ=2 nm) and synthetic sprite spectra from models. We found that while the relative population of N2(B3Πg,v=2−7) in sprites and laboratory produced air glow plasmas are similar, the N2(B3Πg,v=1) vibrational level in sprites is more efficiently populated (in agreement with model predictions) than in laboratory air glow plasmas at similar pressures.

9 págs; 5 figs.; 6 tabs., The effects of cosmic rays on the carriers of the interstellar 3.4 μm absorption band have been investigated in the laboratory. This band is attributed to stretching vibrations of CH3 and CH2 in carbonaceous dust. It is widely observed in the diffuse interstellar medium, but disappears in dense clouds. Destruction of CH3 and CH2 by cosmic rays could become relevant in dense clouds, shielded from the external ultraviolet field. For the simulations, cules, formed by the recombination of H atoms liberated through CH bond breaking, diffuse out of the sample. The CH bond destruction rates derived from the present experiments are in good accordance with those from previous ion irradiation experiments of HAC. The experimental simplicity of electron the 3.4 μm band carriers lie in the 108 yr range and cannot account for the disappearance of this band in dense clouds, which have characteristic lifetimes of 3×107 yr. The results invite a more detailed investigation of the mechanisms of CH bond formation and breaking in the intermediate region between diffuse and dense clouds., This work has been funded by the MINECO of Spain under grant FIS2013-48087-C2-1P, by the MICINN of Spain under grant CDS2009-00038, and by the European project ERC-2013-Syg 610256. G.M. acknowledges MINECO PhD grant BES-2014-069355.

The chloroniumyl cation, HCl+, has been recently identified in space from Herschel’s spectra. A joint analysis of extensive vis-UV spectroscopy emission data together with a few high-resolution and high-accuracy millimiter-wave data provided the necessary rest frequencies to support the astronomical identification. Nevertheless, the analysis did not include any infrared (IR) vibration-rotation data. Furthermore, with the end of the Herschel mission, infrared observations from the ground may be one of the few available means to further study this ion in space. In this work, we provide a set of accurate rovibrational transition wavenumbers as well as a new and improved global fit of vis-UV, IR and millimiter-wave spectroscopy laboratory data, that will aid in future studies of this molecule.

The recent discovery of ArH+ in the interstellar medium has awakened the interest in the chemistry of this ion. In this work, the ion-molecule kinetics of cold plasmas of Ar/H2 is investigated in glow discharges spanning the whole range of [H2]/([H2]+[Ar]) proportions for two pressures, 1.5 and 8 Pa. Ion concentrations are determined by mass spectrometry, and electron temperatures and densities, with Langmuir probes. A kinetic model is used for the interpretation of the results. The selection of experimental conditions evinces relevant changes with plasma pressure in the ion distributions dependence with the H2 fraction, particularly for the major ions: Ar+, ArH+ and H3+. At 1.5 Pa, ArH+ prevails for a wide interval of H2 fractions: 0.3 0.1. The analysis of the data with the kinetic model allows the identification of the sources and sinks of the major ions over the whole range of experimental conditions sampled. Two key factors turn out to be responsible for the different ion distributions observed: the electron temperature, which determines the rate of Ar+ formation and thus of ArH+, and the equilibrium ArH+ + H2 ⇄ H3+ + Ar, which can be strongly dependent of the degree of vibrational excitation of H3+. The results are discussed and compared with previously published data on other Ar/H2 plasmas.

Oral presentation given at the 70th International Symposium on Molecular Spectroscopy, held on June 22-26th, 2015 at The University of Illinois at Urbana-Champaign (United States)., HCl^+ is a key intermediate in the interstellar chemistry of chlorine. It has been recently identified in space from Herschel's spectra and it has also been detected in the laboratory through its optical emission, infrared and mm-wave spectra. Now that Hershchel is decomissioned, further astrophysical studies on this radical ion will likely rely on ground-based observations in the mid-infrared. We have used a difference frequency laser spectrometer coupled to a hollow cathode discharge to measure the absorption spectrum of H35Cl^+ and H37Cl^+ in the v=0-1 band of the ^2Π state with Dopppler limited resolution. The accuracy of the individual measurements (˜ 10 MHz (3σ)) relies on a solid state wavemeter referenced to an iodine-stabilized Ar^+ laser. The new data are being fit using the CALPGM software from JPL, and the current status will be presented.

Astrophysical Ices in the Lab, Workshop, Instituto de Estructura de la Materia, IEM-CSIC, Madrid (Spain), 7-8 March 2016 ; http://www.iem.csic.es/fismol/AILab/program.htm

26 pags. ; 2 tabs. ; 6 figs., The chemistry of low pressure H2 + O2 discharges with different mixture ratios has been studied in a hollow cathode DC reactor. Neutral and positive ion distributions have been measured by mass spectrometry, and Langmuir probes have been used to provide charge densities and electron temperatures. A simple zero order kinetic model including neutral species and positive and negative ions, which takes into account gas-phase and heterogeneous chemistry, has been used to reproduce the global composition of the plasmas over the whole range of mixtures experimentally studied, and allows for the identification of the main physicochemical mechanisms that may explain the experimental results. To our knowledge, no combined experimental and modelling studies of the heavy species kinetics of low pressure H2 + O2 plasmas including ions has been reported before. As expected, apart from the precursors, H2O is detected in considerable amounts. The model also predicts appreciable concentrations of H and O atoms and the OH radical. The relevance of the metastable species O(1D) and O2(a1Δg) is analysed. Concerning the charged species, positive ion distributions are dominated by H3O+ for a wide range of intermediate mixtures, while H3 + and O2 + are the major ions for the higher and lower H2/O2 ratios, respectively. The mixed ions OH+, H2O+ and HO2 + are also observed in small amounts. Negative ions are shown to have a limited relevance in the global chemistry; their main contribution is the reduction of the electron density available for electron impact processes. © 2015 IOP Publishing, This work has been funded by the MCINN of Spain under grants FIS2010-16455, FIS2013- 48087-C2-1-P and the Consolider Astromol, CDS2009-00038. We thank also the European Research Council for additional support under ERC-2013-Syg 610256-NANOCOSMOS. MJR has received funding from the FPI program of the MCINN, and EC from the JdC program of the same ministry.

The low-temperature rotational relaxation of CO in self-collisions and in collisions with the rare-gas atoms Ne and He has been investigated in supersonic expansions with a combination of resonance-enhanced multiphoton ionization (REMPI) spectroscopy and time-of-flight techniques. For the REMPI detection of CO, a novel 2 + 1′ scheme has been employed through the A1 state of CO. From the measured data, average cross sections for rotational relaxation have been derived as a function of temperature in the range 5-100 K. For CO-Ne and CO-He, the relaxation cross sections grow, respectively, from values of ∼20 and 7 Å2 at 100 K to values of ∼65-70 and ∼20 A°2 in the 5-20 K temperature range. The cross section for the relaxation of CO-CO grows from a value close to 40 Å2 at 100 K to a maximum of 60 Å2 at 20 K and then decreases again to 40 Å2 at 5 K. These results are qualitatively similar to those obtained previously with the same technique for N2-N 2, N2-Ne, and N2-He collisions, although in the low-temperature range (T < 20 K) the CO relaxation cross sections are significantly larger than those for N2. Some discrepancies have been found between the present relaxation cross sections for CO-CO and CO-He and the values derived from electron-induced fluorescence experiments. © 2005 American Chemical Society., Financial support through the Ramón y Cajal program. Financial support from the EU Research Training Network “Reaction Dynamics”, Grant HPRNCT-1999-00007.Financial support from the Spanish Ministry of Education through the State Secretary of Education and University. Support from the Plan Andaluz de Investigación (Group FQM-205). Funding by the MEC of Spain under Grants FIS2004-00456 and BQU2002-04627-C02-02

9 pages, 7 figures, 1 table.-- Printed version published Jul 21, 2005., The neutral and charged species present in a direct current (dc) hollow cathode, gas flow, air reactor are experimentally studied by quadrupole mass spectrometry. The degree of ionization of the plasma and the electron mean temperature with decreasing air pressure, for constant discharge current, are measured with a double Langmuir probe. The chemical composition of the plasma changes appreciably over the 3x10(-3) to 5x10(-2) mbar range investigated: at the lowest pressures studied, O2 dissociation is up to 60% and the concentration of NO is half that of N2; concerning ions, NO+ and N2+ are dominant for the whole pressure range. A kinetic model of the plasma including electrons, neutrals, and positive ions is developed to account for the experimental observations; it is consistent with energy balance and predicts that heterogeneous processes are the main source of NO and that the contribution of ions to the global chemistry of neutrals is of minor significance even for the lowest pressures., The SEUID of Spain (Projects FIS2004-00456, FTN2003-08228-C03-03) and C.A.M. (07N/0058/2002) are gratefully acknowledged for financial support.

The transients associated with the ignition and extinction of the cold plasma produced in a low-frequency, square wave modulated, hollow cathode discharge of air are characterized by time resolved mass spectrometry and emission spectroscopy. The time evolution of the concentrations of neutral products measured in the discharge (NO, N2O, N and O) is compared with the predictions of a simple kinetic model previously developed to characterize low-pressure plasmas of N2O, NO and NO2 and a good agreement is found.© 2004 IOP Publishing Ltd, SEUID of Spain (Projects REN2000-1557, FTN2003-08228-C03-03) and CAM (07N/0058/2002)

Complete suppression of amorphous C:H film deposition has been reported for N2/CH4 ratios ∼1, in low-pressure technical plasmas. This finding has been recently used by the authors for the proposal of a possible technique for the inhibition of re-deposited T-containing carbon films at the divertor region of fusion devices. Although several works aiming to the understanding of the underlying physicochemical processes have been published, the complexity of the system is far from being properly described by the proposed models. In the present work, experiments in DC glow discharges at low pressure of H2/CH4/N2 admixtures (90:0–5:0–5) are described. Mass spectrometry of neutral species as well as plasma mass spectrometry for ion detection have been used as the main diagnostics. Several plasma conditions (plasma current, gas composition, etc.) as well as isotopic exchange (H/D) have been investigated. Also, the effect of progressive film growing on the metal walls of the reactor in the composition of gas-phase species has been investigated. It is concluded that wall carbonisation is required to trigger the inhibition process. Ethylene and acetylene are found as the main reaction products. © 2004 Elsevier Ltd, supported by Dirección General de Investigación Científica y Técnica (DGICYT) under Project FTN2000-0915-C03-01, by CAM (Project 07N/0058/2002) and by M.E.C.D. of Spain (Project SB2000-0051)

The transients associated with the ignition and the extinction of the cold plasma produced in a low frequency, square-wave modulated, hollow cathode discharge of nitrogen dioxide are characterized by time resolved emission spectroscopy, mass spectrometry and electrical probes. The temporal evolution of the concentrations of neutral species created or destroyed in the NO 2 discharges are compared with the predictions of a simple kinetic model previously developed for discharges of other nitrogen oxides (N 2O and NO). The physical conditions of pressure, gas flow rate, modulation frequency and electrical current in the NO2 plasma were selected in order to highlight the time-dependent behaviour of some of the stable species formed in the discharge, especially the nitrogen oxide products, whose concentrations show transient maxima. The usefulness of the analysis of the transient results is emphasized as a means to evaluate the relevance of the different elementary processes and as a key to estimate the values of some of the rate constants critical to the modelling.© 2004 IOP Publishing Ltd, Support of the SEUID of Spain (Projects REN2000-1557, FTN2000-0915-C03-03, PB98-0762-C03-02) and CAM (07N/0058/2002)

19 pags. 3 figs., The rotational relaxation of N2 in collisions with He has been investigated in free jets with a combination of resonance-enhanced-multiphoton ionization spectroscopy and time-of-flight techniques. From the measured data, a global cross-section for rotational relaxation has been derived. The cross section grows from a value of ≈8 Å2 at 100 K to ≈18 Å2 at 5-15 K. For the weakest supersonic expansions investigated, a breakdown of the translational equilibrium between He and N2 has been observed, that could be well accounted for by an isentropic jet model and classical collision cross-sections. © 2002 Elsevier Science B.V. All rights reserved., Financed by the Ministry of Science and Technology of Spain under Grants PB98-0762-C03 and REN 2000-1557 CLI and by the European Union through the RTN Reaction Dynamics (HPRN-CT-1999-0007). Support from the Plan Andaluz de Investigación (group FQM-205).

11 págs.; 12 figs.; 6 tabs.; 1 app. Appendix A is available in electronic form at http://www.aanda.org, Context. 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. Aims. We present UV-irradiation experiments of a pure CO2 ice analog. Calibration of the quadrupole mass spectrometer allowed us to quantify the photodesorption of molecules to the gas phase. This information was added to the data provided by the Fourier transform infrared spectrometer on the solid phase to obtain a complete quantitative study of the UV photoprocessing of an ice analog. Methods. 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. Results. 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, with maximum photodesorption yields (Ypd) of ∼1.2 × 10−2 molecules incident photon−1, ∼9.3 × 10−4 molecules incident photon−1, and ∼1.1 × 10−4 molecules incident photon−1, respectively. Conclusions. 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. © ESO 2015, This research was financed by the Spanish MINECO under project AYA2011-29375. R.M.D. benefited from a FPI grant from Spanish MINECO. V.J.H. and I.T. acknowledge financial support from Spanish MINECO under project FIS2013-48087-C2-1-P.

70 ISMS, Champaign-Urbana, Illinois, June 22-26, 2015; http://isms.illinois.edu/2015/, Carbonaceous compounds, both solids and gas-phase molecules, are found in very diverse astronomical mediaa. A significant amount of the elemental carbon is found in small dust grains. This carbonaceous dust, mostly formed in the last stages of evolution of C-rich stars, is the carrier of characteristic IR absorption bands revealing the presence of aliphatic, aromatic and olefinic functional groups in variable proportionsb. Among the various candidate materials investigated as possible carriers of these bands, hydrogenated amorphous carbon (a-C:H) has led to the best agreement with the observations. Carbonaceous grains are processed by H atoms, UV radiation, cosmic rays and interstellar shocks in their passage from asymptotic giant branch stars to planetary nebulae and to the diffuse interstellar medium. The mechanisms of a-C:H production and evolution in astronomical media are presently a subject of intensive investigation. In this work we present a study of the stability of carbonaceous dust analogues generated in He+CH4 radiofrequency discharges. In order to simulate the processing of dust in the interstellar environments, the samples have been subjected to electron bombardment, UV irradiation, and both He and H2 plasma processing. IR spectroscopy is employed to monitor the changes in the structure and composition of the carbonaceous films. aA.G.G.M. Tielens. Rev. Mod. Phys., 85, 1021 (2013) bJ.E. Chiar, A.G.G.M. Tielens, A.J. Adamson and A. Ricca. Astrophys. J., 770, 78 (2013) NOTE

10 pags.; 6 figs.; 4 tabs., © 2015. The American Astronomical Society. All rights reserved. The destruction of solid glycine under irradiation with 2 keV electrons has been investigated by means of IR spectroscopy. Destruction cross sections, radiolysis yields, and half-life doses were determined for samples at 20, 40, 90, and 300 K. The thickness of the irradiated samples was kept below the estimated penetration depth of the electrons. No significant differences were obtained in the experiments below 90 K, but the destruction cross section at 300 K was larger by a factor of 2. The radiolysis yields and half-life doses are in good accordance with recent MeV proton experiments, which confirms that electrons in the keV range can be used to simulate the effects of cosmic rays if the whole sample is effectively irradiated. In the low temperature experiments, electron irradiation leads to the formation of residues. IR absorptions of these residues are assigned to the presence CO2, CO, OCN-, and CN- and possibly to amide bands I to III. The protection of glycine by water ice is also studied. A water ice film of ~150 nm is found to provide efficient shielding against the bombardment of 2 keV electrons. The results of this study show also that current Monte Carlo predictions provide a good global description of electron penetration depths. The lifetimes estimated in this work for various environments ranging from the diffuse interstellar medium to the inner solar system, show that the survival of hypothetical primeval glycine from the solar nebula in present solar system bodies is not very likely., This work has been funded by the MINECO of Spain under grant FIS2013-48087-C2-1 P. Funding from European project ERC-2013-Syg 610256 is also acknowledged.

Gas phase compounds produced in low pressure dc hollow cathode flowing discharges of acetylene, dimethylsulfide (DMS) and dimethyldisulfide (DMDS) have been, by the first time, identified and quantitatively measured through in situ FT-IR absorption spectroscopy. Experimental discharge parameters have been varied in the ranges where stable enough plasmas were produced. A high conversion of precursors to non-volatile compounds is observed. Only diacetylene has been detected in the infrared spectra of acetylene/inert gas discharges, with yields between 3 and 13%. Its appearance indicates that the C 2 H radical is the main intermediate species produced in such discharges. CS 2 , CH 4 and C 2 H 2 have been the most abundant products detected in the infrared spectra of DMS and DMDS plasmas, their maximal yields being in the range 5–20%. The concurrent production of CO, CO 2 and OCS, with yields one to two orders of magnitude lower, must be attributed to oxidation processes of the precursors due to air traces in the discharge cell. No final gaseous compounds, either oxygenated or not, suggesting the production of the CH 3 S radical as intermediate species were detected in these plasmas. The results presented clearly prove that hollow cathode discharges (HCD) produce cold plasmas where high temperature chemistry is conducted.

9 pages, 5 figures, 1 table.-- Printed version published Nov 2002., This work describes a systematic experimental study and kinetic modelling of the steady state and the transients associated with the turn-on and turn-off of a NO hollow cathode discharge. The local charge density and mean electron energy have been determined with a double Langmuir probe. Time-resolved Fourier transform infrared spectroscopy and electron bombardment quadrupole mass spectrometry with ionization by electron impact have been used to measure the gas temperature and the concentrations of the stable molecules present in the discharge: the precursor, NO, the major products, N2, O2, and the minor species NO2 and N2O. Emission spectroscopy has been employed to study the time behaviour of the very reactive nitrogen and oxygen atoms. A model based on a reduced set of kinetic equations including electron dissociation, gas-phase reactions, and gas-surface processes gives a global account of the measured data. From the time-resolved results, electron impact dissociation rate constants for some of the involved species under the conditions of the experiment are estimated. This model is compared with that obtained in previous works on N2O plasmas., The SEUID of Spain (Projects REN2000-1557, PB98-0762-C03-02, FTN2000-0915-C03-03) is gratefully acknowledged for financial support.

University of Illinois, Illinois (USA), June 16 - 20, 2014, The protonated Ar ion 36ArH+ has recently been identified in space,a in the Crab Nebula, from Herschel spectra. Its R(0) and R(1) transitions lie at 617.5 and 1234.6 GHz, respectively, where atmospheric transmission is rather poor, even for a site as good as that of ALMA. As an alternative, especially after the end of the Herschel mission, rovibrational transitions of ArH+ could be observed in absorption against bright background sources such as the galactic center, or other objects. We report on accurate laboratory wavenumber measurements of 19 lines of the v = 1-0 band of 36ArH+ and 38ArH+, using a hollow cathode discharge cell, a difference frequency laser spectrometer and Ar with natural isotopic composition. Of those lines, only eight had been reported before and with much less accuracy.b The data have also been used in a Dunham-type global fit of all published laboratory data (IR and sub-mm) of all isotopologues.

19 págs. ; 9 figs. 1 tab., The effect of UV photon (120–200 nm) and electron (2 keV) irradiation of analogues of interstellar carbonaceous dust and of glycine were investigated by means of IR spectroscopy. Films of hydrogenated amorphous carbon (HAC), taken as dust analogues, were found to be stable under UV photon and electron bombardment. High fluences of photons and electrons, of the order of 1019 cm 2 , were needed for a film depletion of a few percent. UV photons were energetically more effective than electrons for depletion and led to a certain dehydrogenation of the HAC samples, whereas electrons led seemingly to a gradual erosion with no appreciable changes in the hydrocarbon structure. The rates of change observed may be relevant over the lifetime of a diffuse cloud, but cannot account for the rapid changes in hydrocarbon IR bands during the evolution of some proto-planetary nebulae. Glycine samples under the same photon and electron fluxes decay at a much faster rate, but tend usually to an equilibrium value different from zero, especially at low temperatures. Reversible reactions re-forming glycine, or the build-up of less transparent products, could explain this behavior. CO2 and methylamine were identified as UV photoproducts. Electron irradiation led to a gradual disappearance of the glycine layers, also with formation of CO2. No other reaction products were clearly identified. The thicker glycine layers (a few hundred nm) were not wholly depleted, but a film of the order of the electron penetration depth (80 nm), was totally destroyed with an electron fluence of 1 1018 cm 2 . A 60 nm ice layer on top of glycine provided only partial shielding from the 2 keV electrons. From an energetic point of view, 2 keV electrons are less efficient than UV photons and, according to literature data, much less efficient than MeV protons for the destruction of glycine. The use of keV electrons to simulate effects of cosmic rays on analogues of interstellar grains should be taken with care, due to the low penetration depths of electrons in many samples of interest., This work was funded by the MCINN of Spain under grants FIS2010-16455 and CDS2009-00038. M. Jiménez-Redondo acknowledges also funding from the FPI program of the MICINN.

13 pags.; 4 figs., The main characteristics of atomic and molecular beams from gas flow sources and their applications to spectroscopy and gas phase scattering processes are briefly reviewed. The vacuum requirements for the described experimental achievements are emphasised. © 1998 Elsevier Science Ltd. All rights reserved., financed by the DGICYT of Spain under grant PB95-0918-CO2.

The present work describes a systematic experimental investigation of a N2O hollow cathode discharge. The local electron mean energy and density have been determined with a double Langmuir probe. Fourier transform infrared spectroscopy and mass spectrometry have been employed for the measurement of the concentration of the stable species present in the discharge. N2O, N2, O2, and NO are always identified as the main constituents of the discharge plasma. In addition, NO2 is found for the first time in a glow discharge of nitrous oxide. As a plausible explanation, a reaction of NO with oxygen atoms adsorbed on the cathode walls is proposed, although homogeneous reactions of vibrationally excited species cannot be discarded. A model based on a reduced set of kinetic equations including electron dissociation, gas-phase reactions, and gas-surface processes can give a global account of the measured data for all the experimental conditions used. The results are discussed and, when possible, compared to previous works on other types of N2O glow discharges.© 1998 American Chemical Society, DGICYT of Spain (Projects PB94-128, PB95-0918-C03-02) and the Comunidad de Madrid (Project COR0031/94), EC (Contract ERBCHBGCT940551 and Project PL950099)