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The reservoir of sulfur accounting for sulfur depletion in the gas of dense clouds and circumstellar regions is still unclear. One possibility is the formation of sulfur chains, which would be difficult to detect by spectroscopic techniques. This work explores the formation of sulfur chains experimentally, both in pure H$_2$S ice samples and in H$_2$O:H$_2$S ice mixtures. An ultra-high vacuum chamber, ISAC, eqquipped with FTIR and QMS, was used for the experiments. Our results show that the formation of H$_2$S$_x$ species is efficient, not only in pure H$_2$S ice samples, but also in water-rich ice samples. Large sulfur chains are formed more efficiently at low temperatures ($\approx$10 K), while high temperatures ($\approx$50 K) favour the formation of short sulfur chains. Mass spectra of H$_2$S$_x$, x~=~2-6, species are presented for the first time. Their analysis suggests that H$_2$S$_x$ species are favoured in comparison with S$_x$ chains. Nevertheless, the detection of several S$_x^+$ fragments at high temperatures in H$_2$S:H$_2$O ice mixtures suggests the presence of S$_8$ in the irradiated ice samples, which could sublimate from 260~K. ROSINA instrument data from the cometary Rosetta mission detected mass-to-charge ratios 96 and 128. Comparing these detections with our experiments, we propose two alternatives: 1) H$_2$S$_4$ and H$_2$S$_5$ to be responsible of those S$_3^+$ and S$_4^+$ cations, respectively, or 2) S$_8$ species, sublimating and being fragmented in the mass spectrometer. If S$_8$ is the parent molecule, then S$_5^+$ and S$_6^+$ cations could be also detected in future missions by broadening the mass spectrometer range.

The surfaces of icy moons are primarily composed of water ice that can be mixed with other compounds, such as carbon dioxide. The carbon dioxide (CO$_2)$ stretching fundamental band observed on Europa and Ganymede appears to be a combination of several bands that are shifting location from one moon to another. We investigate the cause of the observed shift in the CO$_2$ stretching absorption band experimentally. We also explore the spectral behaviour of CO$_2$ ice by varying the temperature and concentration.} %H$_2$O:CO$_2$ deposition ratios. We analyzed pure CO$_2$ ice and ice mixtures deposited at 10 K under ultra-high vacuum conditions using Fourier-transform infrared (FTIR) spectroscopy and temperature programmed desorption (TPD) experiments. Laboratory ice spectra were compared to JWST observation of Europa's and Ganymede's leading hemispheres. The simulated IR spectra were calculated using density functional theory (DFT) methods, exploring the effect of porosity in CO$_2$ ice. Pure CO$_2$ and CO$_2$-water ice show distinct spectral changes and desorption behaviours at different temperatures, revealing intricate CO$_2$ and H$_2$O interactions. The number of discernible peaks increases from two in pure CO$_2$ to three in CO$_2$-water mixtures., Comment: Accepted for publication in Astronomy & Astrophysics

Acetic acid (CH3COOH) was detected in the gas toward interstellar clouds, hot cores, protostars and comets. Its formation in ice mantles was proposed and acetic acid awaits detection in the infrared spectra of the ice as most other COMs except methanol. The thermal annealing and UV-irradiation of acetic acid in the ice was simulated experimentally in this work under astrophysically relevant conditions. The experiments were performed under ultra-high vacuum conditions. An ice layer was formed by vapor deposition onto a cold substrate, and was warmed up or exposed to UV photons. The ice was monitored by infrared spectroscopy while the molecules desorbing to the gas phase were measured using a quadrupole mass spectrometer. The transformation of the CH3COOH monomers to cyclic dimers occurs at 120 K and the crystal form composed of chain polymers was observed above 160 K during warm-up of the ice. Ice sublimation proceeds at 189 K in our experiments. Upon UV-irradiation simpler species and radicals are formed, which lead to a residue made of complex molecules after warm-up to room temperature. The possible formation of oxalic acid needs to be confirmed. The photodestruction of acetic acid molecules is reduced when mixed with water in the ice. This work may serve to search for the acetic acid photoproducts in lines of sight where this species is detected. A comparison of the reported laboratory infrared spectra with current JWST observations allows to detect or set upper imits on the CH3COOH abundances in interstellar and circumstellar ice mantles., Comment: Accepted to MNRAS

The presence of methanol among the common ice components in interstellar clouds and protostellar envelopes has been confirmed by the James Webb Space Telescope. Methanol is often detected in the gas phase toward lines of sight shielded from UV radiation. We measured the volumetric density of methanol ice, grown under simulated interstellar conditions, and the infrared spectroscopy at different deposition temperatures and during the warm-up. The IR band strengths are provided and the experimental spectra are compared to those computed with a model. The transition from amorphous to crystalline methanol ice was also explored. Finally, we propose new observations of methanol ice at high resolution to probe the methanol ice structure., Comment: 11 pages, 11 figures

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 press

Enceladus, an icy moon of Saturn, possesses an internal water ocean and jets expelling ocean material into space. Cassini investigations indicated that the subsurface ocean could be a habitable environment having a complex interaction with the rocky core. Further investigation of the composition of the plume formed by the jets is necessary to fully understand the ocean, its potential habitability, and what it tells us about Enceladus' origin. Moonraker has been proposed as an ESA M-class mission designed to orbit Saturn and perform multiple flybys of Enceladus, focusing on traversals of the plume. The proposed Moonraker mission consists of an ESA-provided platform, with strong heritage from JUICE and Mars Sample Return, and carrying a suite of instruments dedicated to plume and surface analysis. The nominal Moonraker mission has a duration of 13.5 years. It includes a 23-flyby segment with 189 days allocated for the science phase, and can be expanded with additional segments if resources allow. The mission concept consists in investigating: i) the habitability conditions of present-day Enceladus and its internal ocean, ii) the mechanisms at play for the communication between the internal ocean and the surface of the South Polar Terrain, and iii) the formation conditions of the moon. Moonraker, thanks to state-of-the-art instruments representing a significant improvement over Cassini's payload, would quantify the abundance of key species in the plume, isotopic ratios, and physical parameters of the plume and the surface. Such a mission would pave the way for a possible future landed mission., Comment: Accepted for publication in The Planetary Science Journal

The overabundance of gas molecules in the coldest regions of space point to a non-thermal desorption process. Laboratory simulations show an efficient desorption of CO ice exposed to ultraviolet radiation, known as photodesorption, which decreases for increasing ice deposition temperature. However, the understanding of this abnormal phenomenon has remained elusive. In this work we show the same phenomenon, and in particular, a dramatic drop in the photodesorption yield is observed when the deposition temperature is 19 K and higher. Also the minimum ice thickness that accounts for a constant photodesorption yield of CO ice is deposition temperature dependent, an observation reported here for the first time. We propose that the key parameters that dominate the absorbed photon energy transfer in CO ice, and contribute to the measured photodesorption yields are the energy transfer length, single ice layer contributed desorption yield, and relative effective surface area. This set of parameters should be incorporated in astrophysical models that simulate photodesorption of the top CO-rich ice layer on icy dust populations with the size distribution which is ice thickness related., Comment: 8 pages, 4 figures

In the context of the IRAM 30m Large Program GEMS, we present a study of thioformaldehyde in several starless cores located in star-forming filaments of Taurus, Perseus, and Orion. We investigate the influence of the environmental conditions on the abundances of these molecules in the cores, and the effect of time evolution. We have modelled the observed lines of H2CS, HDCS, and D2CS using the radiative transfer code RADEX. We have also used the chemical code Nautilus to model the evolution of these species depending on the characteristics of the starless cores. We derive column densities and abundances for all the cores. We also derive deuterium fractionation ratios, Dfrac, to determine and compare the evolutionary stage between different parts of each star-forming region. Our results indicate that the north region of the B213 filament in Taurus is more evolved than the south, while the north-eastern part of Perseus presents an earlier evolutionary stage than the south-western zone. Model results also show that Dfrac decreases with the cosmic-ray ionisation rate, while it increases with density and with the degree of sulphur depletion. In particular, we only reproduce the observations when the initial sulphur abundance in the starless cores is at least one order of magnitude lower than the solar elemental sulphur abundance. The progressive increase in HDCS/H2CS and D2CS/H2CS with time makes these ratios powerful tools for deriving the chemical evolutionary stage of starless cores. However, they cannot be used to derive the temperature of these regions, since both ratios present a similar evolution at two different temperature ranges (7-11 K and 15-19 K). Regarding chemistry, (deuterated) thioformaldehyde is mainly formed through gas-phase reactions (double-replacement and neutral-neutral displacement reactions), while surface chemistry plays an important role as a destruction mechanism., Comment: 31 pages, 26 figures

Context. Sulfur is used as a tracer of the evolution from interstellar clouds to stellar systems. However, most of the expected sulfur in molecular clouds remains undetected. Sulfur disappears from the gas phase in two steps. One first depletion occurs during the translucent phase, reducing the gas phase sulfur by 7-40 times, while the following freeze-out step occurs in molecular clouds, reducing it by another order of magnitude. This long-standing dilemma awaits an explanation. Aims. The aim of this study is to understand under which form the missing sulfur is hiding in molecular clouds. Depletion onto dust grains is considered. Methods. Experimental simulations mimicking H2S ice UV-photoprocessing in molecular clouds were conducted. The ice was monitored using infrared spectroscopy and the desorbing molecules were measured by quadrupole mass spectrometry. Theoretical Monte Carlo simulations were performed for interpretation of the experimental results and extrapolation to astrophysical conditions. Results. H2S2 formation was observed during irradiation at 8 K. Molecules H2Sx with x > 2 were also identified and found to desorb during warm-up, along with S2 to S4 species. Larger Sx molecules up to S8 are refractory at room temperature and remained on the substrate forming a residue. Monte Carlo simulations were able to reproduce the molecules desorbing during warming up, and found that residues are chains or sulfur consisting of 6-7 atoms. Conclusions. We propose that S+ in translucent clouds contributes notoriously to S depletion in denser regions by forming long S-chains on dust in few times 10^4 years. We suggest that the S2 to S4 molecules observed in comets are not produced by fragmentation of these large chains. Instead, they probably come either from UV-photoprocessing of H2S-bearing ice produced in molecular clouds or from short S chains formed during the translucent cloud phase, Comment: Accepted to A&A

Hexamethylentetramine has drawn a lot of attention due to its potential to produce prebiotic species. This work aims to gain a better understanding in the chemical processes concerning methylamine under astrophysically relevant conditions. In particular, this work deeps into the formation of N-heterocycles in interstellar ice analogs exposed to UV radiation, which may lead to the formation of prebiotic species. Experimental simulations of interstellar ice analogs were carried out in ISAC. ISAC is an ultra-high vacuum chamber equipped with a cryostat, where gas and vapour species are frozen forming ice samples. Infrared and ultraviolet spectroscopy were used to monitor the solid phase, and quadrupole mass spectrometry served to measure the composition of the gas phase. The variety of species detected after UV irradiation of ices containing methylamine revealed the presence of 12 species which have been already detected in the ISM, being 4 of them typically classified as complex organic molecules: formamide (HCONH2), methyl cyanide (CH$_3$CN), CH$_3$NH and CH$_3$CHNH. Warming up of the irradiated CH$_3$NH$_2$-bearing ice samples lead to the formation of trimethylentriamine (TMT), a N-heterocycle precursor of HMT, and the subsequent synthesis of HMT at temperatures above 230 K.

Gas phase Elemental abundances in Molecular CloudS (GEMS) is an IRAM 30m Large Program designed to estimate the S, C, N, and O depletions and gas ionization degree, X(e-), in a set of star-forming filaments of Taurus, Perseus and Orion. Our immediate goal is to build up a complete 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 (13CO, C18O, HCO+, H13CO+, HC18O+, HCN, H13CN, HNC, HCS+, CS, SO, 34SO, H2S, and OCS) in 244 positions, covering the AV 3 to 100 mag, n(H2) a few 10$^{3}$ to 10$^6$ cm$^{-3}$, and Tk 10 to 30 K ranges in these clouds, avoiding protostars, HII regions, and outflows. A statistical analysis is carried out to identify general trends between different species and with physical parameters. Relations between molecules reveal strong linear correlations which define three different families: (1) 13CO and C18O; (2) H13CO+, HC18O+, H13CN, and HNC; and (3) the S-bearing molecules. The abundances of the CO isotopologs increase with the gas kinetic temperature until TK 15 K. For higher temperatures, the abundance remains constant with a scatter of a factor of 3. The abundances of H13CO+, HC18O+, H13CN, and HNC are well correlated with each other, and all of them decrease with molecular hydrogen density, following the law n(H2)$^{-0.8\pm0.2}$. The abundances of S-bearing species also decrease with n(H2) at a rate of (S-bearing/H)gas n(H2)$^{-0.6\pm0.1}$. 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 C18O abundance is the quantity that better correlates with the cloud mass. We discuss the utility of the 13CO/C18O, HCO+/H13CO+, and H13CO+/H13CN abundance ratios as chemical diagnostics of star formation in external galaxies., Comment: 28 pages, 22 figures. Accepted for publication in A&A

CS is among the most abundant gas-phase S-bearing molecules in cold dark molecular clouds. It is easily observable with several transitions in the millimeter wavelength range, and has been widely used as a tracer of the gas density in the interstellar medium in our Galaxy and external galaxies. Chemical models fail to account for the observed CS abundances when assuming the cosmic value for the elemental abundance of sulfur. The CS+O -> CO + S reaction has been proposed as a relevant CS destruction mechanism at low temperatures, and could explain the discrepancy between models and observations. Its reaction rate has been experimentally measured at temperatures of 150-400 K, but the extrapolation to lower temperatures is doubtful. Here we calculate the CS+O reaction rate at temperatures <150 K which are prevailing in the interstellar medium. We performed ab initio calculations to obtain the three lowest PES of the CS+O system. These PESs are used to study the reaction dynamics, using several methods to eventually calculate the CS+O thermal reaction rates. We compare the results of our theoretical calculations for 150-400 K with those obtained in the laboratory. Our detailed theoretical study on the CS+O reaction, which is in agreement with the experimental data obtained at 150-400 K, demonstrates the reliability of our approach. After a careful analysis at lower temperatures, we find that the rate constant at 10 K is negligible, which is consistent with the extrapolation of experimental data using the Arrhenius expression. We use the updated chemical network to model the sulfur chemistry in TMC1 based on molecular abundances determined from GEMS project observations. In our model, we take into account the expected decrease of the cosmic ray ionization rate along the cloud. The abundance of CS is still overestimated when assuming the cosmic value for the sulfur abundance., Comment: 11 pages, 10 figures, accepted in Astronomy & Astrophysics

Sulphur is one of the most abundant elements in the Universe. Surprisingly, sulphuretted molecules are not as abundant as expected in the interstellar medium, and the identity of the main sulphur reservoir is still an open question. Our goal is to investigate the H$_{2}$S chemistry in dark clouds, as this stable molecule is a potential sulphur reservoir. Using millimeter observations of CS, SO, H$_{2}$S, and their isotopologues, we determine the physical conditions and H$_{2}$S abundances along the cores TMC 1-C, TMC 1-CP, and Barnard 1b. The gas-grain model Nautilus is then used to model the sulphur chemistry and explore the impact of photo-desorption and chemical desorption on the H$_2$S abundance. Our model shows that chemical desorption is the main source of gas-phase H$_2$S in dark cores. The measured H$_{2}$S abundance can only be fitted if we assume that the chemical desorption rate decreases by more than a factor of 10 when $n_{\rm H}>2\times10^{4}$. This change in the desorption rate is consistent with the formation of thick H$_2$O and CO ice mantles on grain surfaces. The observed SO and H$_2$S abundances are in good agreement with our predictions adopting an undepleted value of the sulphur abundance. However, the CS abundance is overestimated by a factor of $5-10$. Along the three cores, atomic S is predicted to be the main sulphur reservoir. We conclude that the gaseous H$_2$S abundance is well reproduced, assuming undepleted sulphur abundance and chemical desorption as the main source of H$_2$S. The behavior of the observed H$_{2}$S abundance suggests a changing desorption efficiency, which would probe the snowline in these cores. Our model, however, overestimates the observed gas-phase CS abundance. Given the uncertainty in the sulphur chemistry, our data are consistent with a cosmic elemental S abundance with an uncertainty of a factor of 10., Comment: 23 pages, 16 figures

At the low temperatures found in the interior of dense clouds and circumstellar regions, along with H$_2$O and smaller amounts of species such as CO, CO$_2$, or CH$_3$OH, the infrared features of CH$_4$ have been observed on icy dust grains. Ultraviolet (UV) photons induce different processes in ice mantles, affecting the molecular abundances detected in the gas-phase. This work aims to understand the processes that occur in a pure CH$_4$ ice mantle submitted to UV irradiation. We studied photon-induced processes for the different photoproducts arising in the ice upon UV irradiation. Experiments were carried out in ISAC, an ultra-high vacuum chamber equipped with a cryostat and an F-type UV-lamp reproducing the secondary UV-field induced by cosmic rays in dense clouds. Infrared spectroscopy and quadrupole mass spectrometry were used to monitor the solid and gas-phase, respectively, during the formation, irradiation, and warm-up of the ice. Direct photodesorption of pure CH$_4$ was not observed. UV photons form CH$_x\cdot$ and H$\cdot$ radicals, leading to photoproducts such as H$_2$, C$_2$H$_2$, C$_2$H$_6$, and C$_3$H$_8$. Evidence for the photodesorption of C$_2$H$_2$ and photochemidesorption of C$_2$H$_6$ and C$_3$H$_8$ was found, the latter species is so far the largest molecule found to photochemidesorb. $^{13}$CH$_4$ experiments were also carried out to confirm the reliability of these results.

CO$_2$ ice has a phase transition at 35 K when its structure changes from amorphous to crystalline. Using Reflection absorption Infrared Spectroscopy (RAIRS), \"Oberg et al. observed that the photodesorption yield of CO$_2$ ice deposited at 60 K and irradiated at 18 K is 40% lower than that of CO$_2$ ice deposited and irradiated at 18 K. In this work, CO$_2$ ices were deposited at 16-60 K and UV-irradiated at 16 K to rule out the temperature effect and figure out the relationship between photodesorption yield and ice structure. IR spectroscopy is a common method used for measurement of the photodesorption yield in ices. We found that undetectable C atoms produced in irradiated CO$_2$ ice can account for 33% of the amount of depleted CO$_2$ molecules in the ice. A quantitative calibration of QMS was therefore performed to convert the measured ion current into photodesorption yield. During various irradiation periods, the dominant photodesorbing species were CO, O$_2$, and CO$_2$, and their photodesorption yields in CO$_2$ ices deposited at different temperature configurations were almost the same, indicating that ice morphology has no effect on the photodesorption yield of CO$_2$ ice. In addition, we found that the lower desorption yield reported by Mart\'in-Dom\'enech et al. is due to a linear relationship between the photodesorption yield and the combination of energy distribution of Microwave-Discharge Hydrogen-flow Lamp (MDHL) and UV absorption cross section of ices., Comment: 11 pages, 11 figures

We study the chemical evolution of H2O:CO:NH3 ice mixtures irradiated with soft X-rays, in the range 250-1250 eV. We identify many nitrogen-bearing molecules such as e.g., OCN-, NH4+ , HNCO, CH3CN, HCONH2, and NH2COCONH2. Several infrared features are compatible with glycine or its isomers. During the irradiation, we detected through mass spectroscopy many species desorbing the ice. Such findings support either the infrared identifications and reveal less abundant species with not clear infrared features. Among them, m/z = 57 has been ascribed to methyl isocyanate (CH3NCO), a molecule of prebiotic relevance, recently detected in protostellar environments. During the warm up after the irradiation, several infrared features including 2168 cm-1 band of OCN-, 1690 cm-1 band of formamide, and the 1590 cm-1 band associated to three different species, HCOO-, CH3NH2 and NH3+CH2COO survive up to room temperature. Interestingly, many high masses have been also detected. Possible candidates are methyl-formate, (m/z = 60, HCOOCH3), ethanediamide (m/z = 88, NH2COCONH2), and N-acetyl-L-aspartic acid (m=z = 175). This latter species is compatible with the presence of the m/z = 43, 70 and 80 fragments. Photo-desorption of organics is relevant for the detection of such species in the gas-phase of cold environments, where organic synthesis in ice mantles should dominate. We estimate the gas-phase enrichment of some selected species in the light of a protoplanetary disc model around young solar-type stars.

Non-thermal desorption of inter- and circum-stellar ice mantles on dust grains, in particular ultraviolet photon-induced desorption, has gained importance in recent years. These processes may account for the observed gas phase abundances of molecules like CO toward cold interstellar clouds. Ice mantle growth results from gas molecules impinging on the dust from all directions and incidence angles. Nevertheless, the effect of the incident angle for deposition on ice photo-desorption rate has not been studied. This work explores the impact on the accretion and photodesorption rates of the incidence angle of CO gas molecules with the cold surface during deposition of a CO ice layer. Infrared spectroscopy monitored CO ice upon deposition at different angles, ultraviolet-irradiation, and subsequent warm-up. Vacuum-ultraviolet spectroscopy and a Ni-mesh measured the emission of the ultraviolet lamp. Molecules ejected from the ice to the gas during irradiation or warm-up were characterized by a quadrupole mass spectrometer. The photodesorption rate of CO ice deposited at 11 K and different incident angles was rather stable between 0 and 45$^{\circ}$. A maximum in the CO photodesorption rate appeared around 70$^{\circ}$-incidence deposition angle. The same deposition angle leads to the maximum surface area of water ice. Although this study of the surface area could not be performed for CO ice, the similar angle dependence in the photodesorption and the ice surface area suggests that they are closely related. Further evidence for a dependence of CO ice morphology on deposition angle is provided by thermal desorption of CO ice experiments.

In dense clouds of the interstellar medium, dust grains are covered by ice mantles, dominated by H$_2$O. CO and CO$_2$ are common ice components observed in infrared spectra, while infrared inactive N$_2$ is expected to be present in the ice. Molecules in the ice can be dissociated, react or desorb by exposure to secondary ultraviolet photons. Thus, different physical scenarios lead to different ice mantle compositions. This work aims to understand the behaviour of $^{13}$CO : N$_2$ and $^{13}$CO$_2$ : N$_2$ ice mixtures submitted to ultraviolet radiation in the laboratory. Photochemical processes and photodesorption were studied for various ratios of the ice components. Experiments were carried out under ultra-high vacuum conditions at 12K. Ices were irradiated with a continuous emission ultraviolet lamp simulating the secondary ultraviolet in dense interstellar clouds. During the irradiation periods, fourier-transform infrared spectroscopy was used for monitoring changes in the ice, and quadrupole mass spectrometry for gas-phase molecules. In irradiated $^{13}$CO$_2$ : N$_2$ ice mixtures, $^{13}$CO, $^{13}$CO$_2$, $^{13}$CO$_3$, O$_2$, and O$_3$ photoproducts were detected in the infrared spectra. N$_2$ molecules also take part in the photochemistry, and N-bearing molecules were also detected: NO, NO$_2$, N$_2$O, and N$_2$O$_4$. Photodesorption rates and their dependence on the presence of N$_2$ were also studied. As it was previously reported, $^{13}$CO and $^{13}$CO$_2$ molecules can transfer photon energy to N$_2$ molecules. As a result, $^{13}$CO and $^{13}$CO$_2$ photodesorption rates decrease as the fraction of N$_2$ increases, while N$_2$ photodesorption is enhanced with respect to the low UV-absorbing pure N$_2$ ice.

We study the photo-desorption occurring in H$_2$O:CO:NH$_3$ ice mixtures irradiated with monochromatic (550 and 900 eV) and broad band (250--1250 eV) soft X-rays generated at the National Synchrotron Radiation Research Center (Hsinchu, Taiwan). We detect many masses photo-desorbing, from atomic hydrogen (m/z = 1) to complex species with m/z = 69 (e.g., C$_3$H$_3$NO, C$_4$H$_5$O, C$_4$H$_7$N), supporting the enrichment of the gas phase. At low number of absorbed photons, substrate-mediated exciton-promoted desorption dominates the photo-desorption yield inducing the release of weakly bound (to the surface of the ice) species; as the number of weakly bound species declines, the photo-desorption yield decrease about one order of magnitude, until porosity effects, reducing the surface/volume ratio, produce a further drop of the yield. We derive an upper limit to the CO photo-desorption yield, that in our experiments varies from 1.4 to 0.007 molecule photon$^{-1}$ in the range $\sim 10^{15} - 10^{20}$~absorbed photons cm$^{-2}$. We apply these findings to a protoplanetary disk model irradiated by a central T~Tauri star.

GEMS is an IRAM 30m Large Program whose aim is determining the elemental depletions and the ionization fraction in a set of prototypical star-forming regions. This paper presents the first results from the prototypical dark cloud TMC 1. Extensive millimeter observations have been carried out with the IRAM 30m telescope (3mm and 2mm) and the 40m Yebes telescope (1.3cm and 7mm) to determine the fractional abundances of CO, HCO+, HCN, CS, SO, HCS+, and N2H+ in three cuts which intersect the dense filament at the well-known positions TMC 1-CP, TMC 1-NH3, and TMC 1-C, covering a visual extinction range from Av~3 to ~20mag. Two phases with differentiated chemistry can be distinguished: i) the translucent envelope with molecular hydrogen densities of (1-5)x10$^3$ cm$^{-3}$; and ii) the dense phase, located at Av>10mag, with molecular hydrogen densities >10$^4$ cm$^{-3}$. Observations and modeling show that the gas phase abundances of C and O progressively decrease along the C+/C/CO transition zone where C/H~8x10$^{-5}$ and C/O~0.8-1, until the beginning of the dense phase at Av~10 mag. This is consistent with the grain temperatures being below the CO evaporation temperature in this region. In the case of sulfur, a strong depletion should occur before the translucent phase where we estimate a S/H~(0.4 - 2.2) x10$^{-6}$, an abundance ~7-40 times lower than the solar value. A second strong depletion must be present during the formation of the thick icy mantles to achieve the values of S/H measured in the dense cold cores (S/H~8x10$^{-8}$). Based on our chemical modeling, we constrain the value of $\zeta_{\rm H_2}$ to ~(0.5 - 1.8) x10$^{-16}$ s$^{-1}$ in the translucent cloud., Comment: 26 pages, 20 figures, A&A in press

Ice mantles detected on the surface of dust grains toward the coldest regions of the interstellar medium can be photoprocessed by the secondary ultraviolet (UV) field present in dense cloud interiors. In this work, we present UV-irradiation experiments under astrophysically relevant conditions of pure NH3 ice samples in an ultra-high vacuum chamber where solid samples were deposited onto a substrate at 8 K. The ice analogs were subsequently photoprocessed with a microwave-discharged hydrogen- flow lamp. The induced radiation and photochemistry led to the production of H2, N2 and N2H4. In addition, photodesorption to the gas phase of the original ice component, NH3, and two of the three detected photoproducts, H2 and N2, was observed thanks to a quadrupole mass spectrometer (QMS). Calibration of the QMS allowed quantifica- tion of the photodesorption yields, leading to Ypd(NH3)=2.1+2.1-1.0 x 10^-3 molecules per incident photon, which remained constant during the whole experiments, while photodesorption of H2 and N2 increased with fluence, pointing toward an indirect photodesorption mecha- nism involving energy transfer for these species. Photodesorption yield of N2 molecules after a fluence equivalent to that experienced by ice mantles in space was similar to that of the NH3 molecules (Ypd (N2) = 1.7+1.7-0.9 x 10^-3 molecules incident photon ).

In regions where stars form, variations in density and temperature can cause gas to freeze-out onto dust grains forming ice mantles, which influences the chemical composition of a cloud. The aim of this paper is to understand in detail the depletion (and desorption) of CO on (from) interstellar dust grains. Experimental simulations were performed under two different (astrophysically relevant) conditions. In parallel, Kinetic Monte Carlo simulations were used to mimic the experimental conditions. In our experiments, CO molecules accrete onto water ice at temperatures below 27 K, with a deposition rate that does not depend on the substrate temperature. During the warm-up phase, the desorption processes do exhibit subtle differences indicating the presence of weakly bound CO molecules, therefore highlighting a low diffusion efficiency. IR measurements following the ice thickness during the TPD confirm that diffusion occurs at temperatures close to the desorption. Applied to astrophysical conditions, in a pre-stellar core, the binding energies of CO molecules, ranging between 300 K and 850 K, depend on the conditions at which CO has been deposited. Because of this wide range of binding energies, the depletion of CO as a function of AV is much less important than initially thought. The weakly bound molecules, easily released into the gas phase through evaporation, change the balance between accretion and desorption, which result in a larger abundance of CO at high extinctions. In addition, weakly bound CO molecules are also be more mobile, and this could increase the reactivity within interstellar ices., Comment: Accepted in ApJ

The processing of energetic photons on bare silicate grains was simulated experimentally on silicate films submitted to soft X-rays of energies up to 1.25 keV. The silicate material was prepared by means of a microwave assisted solgel technique. Its chemical composition reflects the Mg2SiO4 stoichiometry with residual impurities due to the synthesis method. The experiments were performed using the spherical grating monochromator beamline at the National Synchrotron Radiation Research Center in Taiwan. We found that soft X-ray irradiation induces structural changes that can be interpreted as an amorphization of the processed silicate material. The present results may have relevant implications in the evolution of silicate materials in X-ray irradiated protoplanetary disks., Comment: 13 pages, 7 figures

Methanol and formaldehyde are two simple organic molecules that are ubiquitously detected in the interstellar medium. An origin in the solid phase and a subsequent nonthermal desorption into the gas phase is often invoked to explain their abundances in some of the environments where they are found. Experimental simulations under astrophysically relevant conditions have been carried out to find a suitable mechanism for that process. We explore the in situ formation and subsequent photon-induced desorption of these species, studying the UV photoprocessing of pure ethanol ice, and a more realistic binary H2O:CH4 ice analog. Ice samples deposited onto an infrared transparent window at 8 K were UV-irradiated using a microwave-discharged hydrogen flow lamp. Evidence of photochemical production of these two species and subsequent UV-photon-induced desorption into the gas phase were searched for by means of a Fourier transform infrared spectrometer and a quadrupole mass spectrometer, respectively. Formation of CH3OH was only observed during photoprocessing of the H2O:CH4 ice analog, but no photon-induced desorption was detected. Photochemical production of H2CO was observed in both series of experiments. Photochemidesorption of formaldehyde, i.e., photon-induced formation on the ice surface and inmediate desorption, was observed, with a yield of 4.4 x 10-4 (molecules/incident photon) when the H2O:CH4 ice analogs were photoprocessed. While certain C-bearing species, in particular H2CO, were found to desorb upon irradiation, nonthermal desorption of CH3OH was not observed. So far, there is no experimental evidence of any efficient CH3 OH desorption induced by UV photons.

A fraction of the missing sulfur in dense clouds and circumstellar regions could be in the form of three species not yet de- tected in the interstellar medium: H2S2, HS2, and S2 according to experimental simulations performed under astrophysically relevant conditions. These S-S bonded molecules can be formed by the energetic processing of H2S-bearing ice mantles on dust grains, and subsequently desorb to the gas phase. The detection of these species could partially solve the sulfur depletion problem, and would help to improve our knowledge of the poorly known chemistry of sulfur in the interstellar medium. To this purpose we performed dedicated ground-based observations toward the low-mass warm core IRAS16293-2422. Observations in the submillimeter regime were obtained with the APEX 12 m telescope during 15 hours of observation, targeting a wide selection of the predicted rotational transitions of the three molecules. The 1{\sigma} noise rms values were extracted in the spectral regions where the targeted species should have been detected. These values were a factor of 2-7 lower than those reached by previous observations toward the same source, and allowed us to estimate a 1{\sigma} upper limit to their molecular abundances of 8.1E-9 , 1.1E-8 , and 2.9E-7 relative to H2, for H2S2, HS2, and S2, respectively. The upper limit abundances of the three molecules containing the S2 unit are up to two orders of magnitude lower than the H2S abundance in the source, and one order of magnitude lower than the expected abundances from the experimental simulations using ice analogs. Subsequent gas-phase chemistry after desorption could lower the abundances of the three species to undetectable levels in our observations.

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.

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.

We measure the band strengths in the far-infrared region of interstellar ice analogs of astrophysically relevant species, such as H$_2$O, CO$_2$, CH$_3$OH, and NH$_3$, deposited at low temperature (8-10 $\mathrm{K}$), followed by warm-up, to induce amorphous-crystalline phase transitions when relevant. The spectra of pure H$_2$O, NH$_3$, and CH$_3$OH ices have been measured in the near-, mid- and far-infrared spectroscopic regions using the Interstellar Astrochemistry Chamber (ISAC) ultra-high-vacuum setup. In addition, far-infrared spectra of NH$_3$ and CO$_2$ were measured using a different set-up equipped with a bolometer detector. Band strengths in the far-infrared region were estimated using the corresponding near- and mid-infrared values as a reference. We also performed theoretical calculations of the amorphous and crystalline structures of these molecules using solid state computational programs at density functional theory (DFT) level. Vibrational assignment and mode intensities for these ices were predicted. Infrared band strengths in the 25-500 ${\mu}$m range have been determined for the considered ice samples by direct comparison in the near- and mid-infrared regions. Our values were compared to those we calculated from the literature complex index of refraction. We found differences of a factor of two between the two sets of values. The calculated far-infrared band strengths provide a benchmark for interpreting the observational data from future space telescope missions, allowing the estimation of the ice column densities., Comment: Key words. astrochemistry -- methods: laboratory: solid state -- ISM: molecules -- techniques: spectroscopic -- infrared: ISM

This paper reports the first measurements of solid-phase vacuum-ultraviolet (VUV) absorption cross-sections of heavy isotopologues present in icy dust grain mantles of dense interstellar clouds and cold circumstellar environments. Pure ices composed of D2O, CD3OD, 13CO2, and 15N15N were deposited at 8 K, a value similar to the coldest dust temperatures in space. The column density of the ice samples was 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 as the VUV source. Prior to this work, we have recently submitted a similar study of the light isotopologues (Cruz-Diaz, Mu\~noz Caro and Chen). The VUV spectra are compared to those of the light isotopologues in the solid phase, and to the gas phase spectra of the same molecules. Our study is expected to improve very significantly the models that estimate the VUV absorption of ice mantles in space, which have often used the available gas phase data as an approximation of the absorption cross sections of the molecular ice components. We will show that this work has also important implications for the estimation of the photodesorption rates per absorbed photon in the ice., Comment: 7 pages, 4 figures, 3 tables

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 tables

The VUV absorption cross sections of most molecular solids present in interstellar ice mantles with the exception of H2O, NH3, and CO2 have not been reported yet. Models of ice photoprocessing depend on the VUV absorption cross section of the ice to estimate the penetration depth and radiation dose, and in the past, gas phase cross section values were used as an approximation. We aim to estimate the VUV absorption cross section of molecular ice components. Pure ices composed of CO, H2O, CH3OH, NH3, or H2S were deposited at 8 K. The column density of the ice samples was 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 provide VUV absorption cross sections of the reported molecular ices. Our results agree with those previously reported for H2O and NH3 ices. Vacuum-UV absorption cross section of CH3OH, CO, and H2S in solid phase are reported for the first time. H2S presents the highest absorption in the 120-160 nm range. Our method allows fast and readily available VUV spectroscopy of ices without the need to use a synchrotron beamline. We found that the ice absorption cross sections can be very different from the gas-phase values, and therefore, our data will significantly improve models that simulate the VUV photoprocessing and photodesorption of ice mantles. Photodesorption rates of pure ices, expressed in molecules per absorbed photon, can be derived from our data., Comment: 10 pages

The main goal of this work is to compare the effects induced in ices of astrophysical relevance by high-energy ions, simulating cosmic rays, and by vacuum ultraviolet (UV) photons. This comparison relies on in situ infrared spectroscopy of irradiated CH3OH:NH3 ice. Swift heavy ions were provided by the GANIL accelerator. The source of UV was a microwave-stimulated hydrogen flow discharge lamp. The deposited energy doses were similar for ion beams and UV photons to allow a direct comparison. A variety of organic species was detected during irradiation and later during ice warm-up. These products are common to ion and UV irradiation for doses up to a few tens of eV per molecule. Only the relative abundance of the CO product, after ice irradiation, was clearly higher in the ion irradiation experiments. For some ice mixture compositions, the irradiation products formed depend only weakly on the type of irradiation, swift heavy ions, or UV photons. This simplifies the chemical modeling of energetic ice processing in space., Comment: 9 pages, 9 figures, 2 tables, accepted in A&A

We report on the discovery of methyl acetate, CH3COOCH3, through the detection of a large number of rotational lines from each one of the spin states of the molecule: AA species (A1 or A2), EA species (E1), AE species (E2), EE species (E3 or E4). We also report the detection, for the first time in space, of the $gauche$ conformer of ethyl formate, CH3CH2OCOH, in the same source. The trans conformer is also detected for the first time outside the galactic center source SgrB2. From the derived velocity of the emission of methyl acetate we conclude that it arises mainly from the compact ridge region with a total column density of (4.2+-0.5)E15 cm(-2). The derived rotational temperature is 150 K. The column density for each conformer of ethyl formate, trans and gauche, is (4.5+-1.0)E14 cm(-2). Their abundance ratio indicates a kinetic temperature of 135 K for the emitting gas and suggests that gas phase reactions could participate efficiently in the formation of both conformers in addition to cold ice mantle reactions on the surface of dust grains., Comment: Accepted for publication in ApJL

This work aims to study the unexplained sulfur depletion observed toward dense clouds and protostars. We made simulation experiments of the UV-photoprocessing and sublimation of H2S and H2S:H2O ice in dense clouds and circumstellar regions, using the Interstellar Astrochemistry Chamber (ISAC), a state-of-the-art ultra-high-vacuum setup. The ice was monitored in situ by mid-infrared spectroscopy in transmittance. Temperature-programmed desorption (TPD) of the ice was performed using a quadrupole mass spectrometer (QMS) to detect the volatiles desorbing from the ice. Comparing our laboratory data to infrared observations of protostars we obtained a more accurate upper limit of the abundance of H2S ice toward these objects. We determined the desorption temperature of H2S ice, which depends on the initial H2S:H2O ratio. UV-photoprocessing of H2S:H2O ice led to the formation of several species. Among them, H2S2 was found to photodissociate forming S2 and, by elongation, other species up to S8, which are refractory at room temperature. A large fraction of the missing sulfur in dense clouds and circumstellar regions could thus be polymeric sulfur residing in dust grains., Comment: 11 pages, 19 figures

This paper introduces AntNet, a novel approach to the adaptive learning of routing tables in communications networks. AntNet is a distributed, mobile agents based Monte Carlo system that was inspired by recent work on the ant colony metaphor for solving optimization problems. AntNet's agents concurrently explore the network and exchange collected information. The communication among the agents is indirect and asynchronous, mediated by the network itself. This form of communication is typical of social insects and is called stigmergy. We compare our algorithm with six state-of-the-art routing algorithms coming from the telecommunications and machine learning fields. The algorithms' performance is evaluated over a set of realistic testbeds. We run many experiments over real and artificial IP datagram networks with increasing number of nodes and under several paradigmatic spatial and temporal traffic distributions. Results are very encouraging. AntNet showed superior performance under all the experimental conditions with respect to its competitors. We analyze the main characteristics of the algorithm and try to explain the reasons for its superiority.

We present ESO - Very Large Telescope and ESA - Infrared Space Observatory 3 to 4 $\mu$m spectra of Seyfert 2 nuclei as compared to our galactic center lines of sight. The diffuse interstellar medium probed in both environments displays the characteristic 3.4 $\mu$m aliphatic CH stretch absorptions of refractory carbonaceous material. The profile of this absorption feature is similar in all sources, indicating the CH$_2$/CH$_3$ ratios of the carbon chains present in the refractory components of the grains are the same in Seyfert 2 inner regions. At longer wavelengths the circumstellar contamination of most of the galactic lines of sight precludes the identification of other absorption bands arising from the groups constitutive of the aliphatics seen at 3.4 $\mu$m. The clearer continuum produced by the Seyfert 2 nuclei represents promising lines of sight to constrain the existence or absence of strongly infrared active chemical groups such as the carbonyl one, important to understand the role of oxygen insertion in interstellar grains. The Spitzer Space Telescope spectrometer will soon allow one to investigate the importance of aliphatics on a much larger extragalactic sample., Comment: 10 pages. Accepted for publication on April 30th 2004 in Astronomy and Astrophysics