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22 pags., 8 figs., 1 tab., Massive stars disrupt their natal molecular cloud material through radiative and mechanical feedback processes. These processes have profound effects on the evolution of interstellar matter in our Galaxy and throughout the universe, from the era of vigorous star formation at redshifts of 1-3 to the present day. The dominant feedback processes can be probed by observations of the Photo-Dissociation Regions (PDRs) where the far-ultraviolet photons of massive stars create warm regions of gas and dust in the neutral atomic and molecular gas. PDR emission provides a unique tool to study in detail the physical and chemical processes that are relevant for most of the mass in inter-and circumstellar media including diffuse clouds, proto-planetary disks, and molecular cloud surfaces, globules, planetary nebulae, and star-forming regions. PDR emission dominates the infrared (IR) spectra of star-forming galaxies. Most of the Galactic and extragalactic observations obtained with the James Webb Space Telescope (JWST) will therefore arise in PDR emission. In this paper we present an Early Release Science program using the MIRI, NIRSpec, and NIRCam instruments dedicated to the observations of an emblematic and nearby PDR: the Orion Bar. These early JWST observations will provide template data sets designed to identify key PDR characteristics in JWST observations. These data will serve to benchmark PDR models and extend them into the JWST era. We also present the Science-Enabling products that we will provide to the community. These template data sets and Science-Enabling products will guide the preparation of future proposals on star-forming regions in our Galaxy and beyond and will facilitate data analysis and interpretation of forthcoming JWST observations., Support for JWST-ERS program ID 1288 was provided through grants from the STScI under NASA contract NAS5-03127 to STScI (K.G., D.V.D.P., M.R.), Univ. of Maryland (M.W., M.P.), Univ. of Michigan (E.B., F.A.), and Univ. of Toledo (T.S.-Y.L.). O.B. and E.H. are supported by the Programme National “Physique et Chimie du Milieu Interstellaire” (PCMI) of CNRS/INSU with INC/INP co-funded by CEA and CNES, and through APR grants 6315 and 6410 provided by CNES. E. P. and J.C. acknowledge support from the National Science and Engineering Council of Canada (NSERC) Discovery Grant program (RGPIN-2020-06434 and RGPIN-2021-04197 respectively). E.P. acknowledges support from a Western Strategic Support Accelerator Grant (ROLA ID 0000050636). J.R.G. and S.C. thank the Spanish MCINN for funding support under grant PID2019-106110GB-I00. Work by M.R. and Y.O. is carried out within the Collaborative Research Centre 956, subproject C1, funded by the Deutsche Forschungsgemeinschaft (DFG)—project ID 184018867. T.O. acknowledges support from JSPS Bilateral Program, grant No. 120219939. M.P. and M.W. acknowledge support from NASA Astrophysics Data Analysis Program award #80NSSC19K0573. C.B. is grateful for an appointment at NASA Ames Research Center through the San José State University Research Foundation (NNX17AJ88A) and acknowledges support from the Internal Scientist Funding Model (ISFM) Directed Work Package at NASA Ames titled: “Laboratory Astrophysics—The NASA Ames PAH IR Spectroscopic Database.”

Water ice exists on many objects in space. The most abundant icy species, among them water, are present in the icy satellites of the outer Solar System giant planets. The nuclei of comets, which are mainly composed of water ice, give another example of its abundance. In the interstellar medium (ISM), ice mantles, formed by molecular species sticking on dust grains, consist mainly of water ice. All these objects are exposed to ionizing radiation like ions, UV photons, and electrons. Sputtering of atoms, molecules, ions, and radicals from icy surfaces may populate and maintain exospheres of icy objects in the Solar System. In other respects, ionized hydrides such as OH+, H2O+, and H3O+ have been detected in the gas phase in star-forming regions. Interactions with cosmic rays could be an additional explanation to the current models for the formation of those species. In fact, laboratory simulations showed that the main components of the sputtered ionic species from water ice are oxygen hydrides. In this work, water ice targets were irradiated at several temperatures (10-200 K) by 90 keV O6+ ions, yielding an electronic stopping power of about 12 eV/A, when the nuclear stopping power is comparable to the electronic stopping power. Sputtering of secondary ions after bombardment of the ice target was analyzed by time-of-flight mass spectrometry (TOF-SIMS). Besides hydrogen ions (H+, H2+, H3+), also O+, O2+, OH+, (H2O)+, and clusters of (H2O)nH+ with n = 1-8 are emitted. Our results show a progressive yield decrease with increasing temperature of all of the detected species. This is related to the structure of the ice: the ionic sputtering yield for crystalline ice is much lower than for an amorphous ice. For instance, amorphous ice at 10 K exhibits a yield of the order of 2 × 10-6 secondary (H2O)nH+ hydride ions/projectile (with n = 1-8). As the temperature is increasing toward the phase transition to crystalline ice, the yields decrease by about one order of magnitude.

Context. Reliable, directly measured optical properties of astrophysical ice analogues in the infrared and terahertz (THz) range are missing from the literature. These parameters are of great importance to model the dust continuum radiative transfer in dense and cold regions, where thick ice mantles are present, and are necessary for the interpretation of future observations planned in the far-infrared region. Aims: Coherent THz radiation allows for direct measurement of the complex dielectric function (refractive index) of astrophysically relevant ice species in the THz range. Methods: We recorded the time-domain waveforms and the frequency-domain spectra of reference samples of CO ice, deposited at a temperature of 28.5 K and annealed to 33 K at different thicknesses. We developed a new algorithm to reconstruct the real and imaginary parts of the refractive index from the time-domain THz data. Results: The complex refractive index in the wavelength range 1 mm-150 μm (0.3-2.0 THz) was determined for the studied ice samples, and this index was compared with available data found in the literature. Conclusions: The developed algorithm of reconstructing the real and imaginary parts of the refractive index from the time-domain THz data enables us, for the first time, to determine the optical properties of astrophysical ice analogues without using the Kramers-Kronig relations. The obtained data provide a benchmark to interpret the observational data from current ground-based facilities as well as future space telescope missions, and we used these data to estimate the opacities of the dust grains in presence of CO ice mantles. The data plotted in Fig. 6 are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/cat/J/A+A/629/A112

The comparison between astronomical spectra and laboratory experiments is fundamental to spread light on the structure and composition of ices found in interstellar dense molecular clouds and in Solar system bodies. Water is among the most abundant solid-phase species observed in these environments, and several attempts have been made to investigate the presence of its solid-phase isotopologues. In particular, the detection of the O-D stretching mode band at 4.1 μm due to both D2O and HDO within icy grain mantles is still under debate, and no detection has been reported about the presence of these species within icy bodies in the Solar system yet. In the near future, an important contribution could derive from the data acquired in the O-D stretching mode spectral range by the sensitive instruments on board the James Webb Space Telescope. With this in mind, we performed several laboratory experiments to study the O-D stretching mode band in solid mixtures containing water and deuterated water deposited in the temperature range between 17 and 155 K, in order to simulate astrophysical relevant conditions. Furthermore, samples have been studied at various temperature and irradiated with energetic ions (200 keV H^+) in order to study the effects induced by both thermal and energetic processing. Our results provide some constraints on the detection of the 4.1 μm band in astronomical environments.

Silicates are the dominant surface material of many Solar System objects, which are exposed to ion bombardment by solar wind ions and cosmic rays. Induced physico-chemical processes include sputtering which can contribute to the formation of an exosphere. We have measured sputtering yields and velocity spectra of secondary ions ejected from nepheline, an aluminosilicate thought to be a good analogue for Mercury's surface, as a laboratory approach to understand the evolution of silicate surfaces and the presence of Na and K vapor in the exosphere. Experiments were performed with highly charged ion beams (keV/u–MeV/u) delivered by GANIL using an imaging XY-TOF-SIMS device under UHV conditions. The fluence dependence of sputtering yields gives information about the evolution of surface stoichiometry during irradiation. From the energy distributions N(E) of sputtered particles, the fraction of particles which could escape from the gravitational field of Mercury, and of those falling back and possibly contributing to populate the exosphere can be roughly estimated.

Astrophysical ices are exposed to different radiation fields including photons, electrons and ions. The latter stem from interstellar cosmic rays (CR), the solar and stellar winds, shock waves or are trapped in the magnetospheres of giant planets. We briefly discuss the physics of energy deposition by ion ir radiation in condensed matter and experimental methods to study the induced effects. We then present results on radiation effects such as sputtering, amorphisation and compaction, dissociation of molecules, formation of new molecular species after radiolysis and by implantation of ions. The formation and radio-resistance of organic molecules, related to the question of the initial conditions for the emergence of life, are briefly discussed. This review is not meant to be comprehensive, but rather focusses on recent findings, with special emphasis on experiments with heavy multiply charged ion beams. These experiments aim in particular at simulating the effects of CRs on icy grains in dense molecular clouds, and on the formation of molecules on icy bodies in the Solar System.

In this paper we present the formation of carbon nanowires (polyynes and polycumulenes) in the solid state by ion irradiation of frozen hydrocarbons (C6H6 and C2H2). Irradiations have been performed using H+ ions in the 100’s keV energy regime using fluences up to 5 × 1014 ions/cm2. Beyond the intrinsic significance of these results in the field of material science, this work has been motivated by the fact that ion beam irradiation of hydrocarbon ices is one of the most important process thought to happen in several extraterrestrial environments where many spectroscopic features of polyyne molecules have been identified.

The detection of Energetic Neutral Particles (ENP) above 10 eV can unequivocally relate a surface-bound exosphere to surface features and can monitor instantaneously the effect of plasma precipitation onto the surface. In the framework of a mission to Jupiter's moons, 2D imaging of plasma precipitation will provide important information on the plasma circulation at the orbits of the moons. Furthermore, a joint measurement of precipitating ions will permit an estimation of the efficiency of the release process. Coupled measurements of ENP and gas composition will improve our knowledge of surface release mechanisms. Ganymede's and Europa's Neutral Imaging Experiment (GENIE) is a high-angular-resolution detector, based on the ToF (Time of Flight) technique, that can detect ENP (energy range >10 eV-few keV) in the Jupiter environment thanks to an innovative design and technology. Its objective is to map the sites of origin of the ENP of the icy moons' exospheres to investigate the interaction between the surface and the environment. Finally, coupling GENIE with an ion sensor and a mass spectrometer will be an outstanding opportunity to better understand the magnetosphere-moon coupling within the Jupiter system and compare the surface interaction with plasma in the diverse moons. In this paper, the scientific objectives and requirements of ENP detection are summarized and the description of the innovative design concept of GENIE is given, together with the signal and background noise simulation.

Inter- and circumstellar ices comprise different molecules accreted on cold dust particles. These icy dust grains provide a molecule reservoir where particles can interact and react. As the grain acts as a third body, capable of absorbing energy, icy surfaces in space have a catalytic effect. Chemical reactions are triggered by a number of possible processes; (i) irradiation by light, typically UV photons from the interstellar radiation field and Ly-α radiation emitted by excited hydrogen, but also X-rays, (ii) bombardment by particles, free atoms (most noticeably hydrogen, but also N, C, O and D-atoms), electrons, low energy ions and cosmic rays, and (iii) thermal processing. All these effects cause ices to (photo)desorb, induce fragmentation or ionization in the ice, and eventual recombination will make molecules to react and to form more and more complex species. The effects of this solid state astrochemistry are observed by astronomers; nearly 180 different molecules (not including isotopologues) have been unambiguously identified in the inter- and circumstellar medium, and the abundances of a substantial part of these species cannot be explained by gas phase reaction schemes only and must involve solid state chemistry. Icy dust grains in space experience different chemical stages. In the diffuse medium grains are barely covered by molecules, but upon gravitational collapse and darkening of the cloud, temperatures drop and dust grains start acting as micrometer sized cryopumps. More and more species accrete, until even the most volatile species are frozen. In parallel (non)energetic processing can take place, particularly during planet and star formation when radiation and particle fluxes are intense. The physical and chemical properties of ice clearly provide a snapshotroot to characterize the cosmological chemical evolution. In order to fully interpret the astronomical observations, therefore, dedicated laboratory experiments are needed that simulate dust grain formation and processing as well as ice mantle chemistry under astronomical conditions and in full control of the relevant parameters; ice morphology (i.e., structure), composition, temperature, UV and particle fluxes, etc., yielding parameters that can be used for astrochemical modeling and for comparison with the observations. This is the topic of the present manuscript. Laboratory experiments simulating the conditions in space are conducted for decades all over the world, but particularly in recent years new techniques have made it possible to study reactions involving inter- and circumstellar dust and ice analogues at an unprecedented level of detail. Whereas in the past “top-down scenarios” allowed to conclude on the importance of the solid state for the chemical enrichment of space, presently “bottom-up approaches” make it possible to fully quantify the involved reactions, and to provide information on processes at the molecular level. The recent progress in the field of “solid state laboratory astrophysics” is a consequence of the use of ultra high vacuum systems, of new radiation sources, such as synchrotrons and laser systems that allow extensions to wavelength domains that long have not been accessible, including the THz domain, and the use of highly sensitive gas phase detection techniques, explicitly applied to characterize the solid state such as fluorescence, luminescence, cavity ring-down spectroscopy and sophisticated mass spectrometric techniques. This paper presents an overview of the techniques being used in astrochemical laboratories worldwide, but it is incomplete in the sense that it summarizes the outcome of a 3-day workshop of the authors in November 2012 (at the Observatoire de Meudon in France), with several laboratories represented, but not all. The paper references earlier work, but it is incomplete with regard to latest developments of techniques used in laboratories not represented at the workshop.

Context. Sulfur is an abundant element in the cosmos and it is thus an important contributor to astrochemistry in the interstellar medium and in the solar system. Astronomical observations of the gas and of the solid phases in the dense interstellar/circumstellar regions have evidenced that sulfur is underabundant. The hypothesis to explain such a circumstance is that it is incorporated in some species in the solid phase (I.e. as frozen gases and/or refractory solids) and/or in the gas phase, which for different reasons have not been observed so far. Aims: Here we wish to give a contribution to the field by studying the chemistry induced by thermal and energetic processing of frozen mixtures of sulfur dioxide (one of the most abundant sulfur-bearing molecules observed so far) and water. Methods: We present the results of a series of laboratory experiments concerning thermal processing of different H2O:SO2 mixtures and ion bombardment (30 keV He+) of the same mixtures. We used in situ Fourier transform infrared (FTIR) spectroscopy to investigate the induced effects. Results: The results indicate that ionic species such as HSO, HSO, and S2O are easily produced. Energetic processing also produces SO3 polymers and a sulfurous refractory residue. Conclusions: The produced ionic species exhibit spectral features in a region that, in astronomical spectra of dense molecular clouds, is dominated by strong silicate absorption. However, such a dominant feature is associated with some spectral features, some of which have not yet been identified. We suggest adding the sulfur-bearing ionic species to the list of candidates to help explain some of those features. In addition, we suggest that once expelled in the gas phase by sublimation, due to the temperature increase, and/or by non-thermal erosion those species would constitute a class of molecular ions not detected so far. We also suggest that molecular sulfur-bearing ions could be present on the surfaces and/or in the atmospheres of several objects in the solar system, for example icy satellites of the giant planets and comets.

Methyl formate is a complex organic molecule considered potentially relevant as precursor of biologically active molecules. It has been observed in several astrophysical environments, such as hot cores, hot corinos, and comets. The processes that drive the formation of molecules in cometary ices are poorly understood. In particular it is not yet clear if molecules are directly accreted from the pre-solar nebula to form comets or are formed after accretion. The present work analyzes the possible role of cosmic ion irradiation and radioactive decay in methyl formate formation in methanol-bearing ices. The results indicate that cosmic ion irradiation can account for about 12% of the methyl formate observed in comet Hale–Bopp, while radioactive decay can account for about 6% of this amount. The need of new data coming from earth based and space observational projects as well as from laboratory experiments is outlined.

Context. Space infrared observations with ISO-SWS and Spitzer telescopes have clearly shown that solid carbon dioxide (CO2 )i s ubiquitous and abundant along the line of sight to quiescent clouds and star forming regions. Due to the CO2 low gas-phase abundance, it is suggested that CO2 is synthesized on grains after energetic processing of icy mantles and/or surface reactions. Aims. We study quantitatively the abundance of carbon dioxide synthesized from ice mixtures of astrophysical relevance induced by ion irradiation at low temperature. We compare the CO2 stretching and bending-mode band profiles observed towards some young stellar objects (YSOs) for which infrared spectra exist. Methods. Using a high vacuum experimental setup, the effects induced by fast ions (30−200 keV) on several ice mixtures of astrophysical interest are investigated. Chemical and structural modifications of the ice samples that form new molecular species are analyzed using infrared spectroscopy. The formation cross section of solid CO2 is estimated from the increase in column density as a function of the dose fitting of experimental data with an exponential curve. Results. Our laboratory experiments showed that carbon dioxide is formed after irradiation of ice mixtures containing C- and O-bearing molecules. Furthermore, when the same amount of energy is released into the icy sample, a larger amount of CO2 is formed in H2O-rich mixtures in agreement with previous studies. We also found that the CO2 stretching and bending mode band profiles depend on the mixture and temperature of the ice sample. We found that the amount of carbon dioxide formed after ion irradiation can account for the observed carbon dioxide towards YSOs. Furthermore, we discovered that laboratory spectra are a good spectroscopic analogue of the interstellar features. Conclusions. Even if the comparison between laboratory and observed spectra presented here cannot be considered unique and complete, our results quantitatively support the hypothesis that interstellar solid CO2 forms after ion irradiation and UV photolysis of icy mantles.

Ices in the solar system are observed on the surface of planets, satellites, comets and asteroids where they are continuously subordinate at particle fluxes (cosmic ions, solar wind and charged particles caught in the magnetosphere of the planets) that deeply modify their physical and structural properties. Each incoming ion destroys molecular bonds producing fragments that, by recombination, form new molecules also different from the original ones. Moreover, if the incoming ion is reactive (H+, On+, Sn+, etc.), it can concur to the formation of new molecules. Those effects can be studied by laboratory experiments where, with some limitation, it is possible to reproduce the astrophysical environments of planetary ices. In this work, we describe some experiments of 15–100 keV H+ and He+ implantation in pure sulfur dioxide (SO2) at 16 and 80 K and carbon dioxide (CO2) at 16 K ices aimed to search for the formation of new molecules. Among other results we confirm that carbonic acid (H2CO3) is formed after H-implantation in CO2, vice versa H-implantation in SO2 at both temperatures does not produce measurable quantity of sulfurous acid (H2SO3). The results are discussed in the light of their relevance to the chemistry of some solar system objects, particularly of Io, the innermost of Jupiter's Galilean satellites, that exhibits a surface very rich in frost SO2 and it is continuously bombarded with H+ ions caught in Jupiter's magnetosphere.

Solid objects in space (interstellar grains, comets, interplanetary dust particles, etc.) are continuously exposed to energetic processes, such as cosmic ion irradiation, that influence their evolution. In this paper we present an experimental study, carried out by Raman spectroscopy, of the effects induced by ion irradiation on frozen ices and refractory materials. If the irradiated ice mixture contains a relevant amount of carbon atoms, the ice is converted into an organic residue (stable at room temperature), which at high irradiation dose evolves toward a hydrogenated amorphous carbon. Here we show that material similar to that produced in the laboratory by ion irradiation of frozen ice mixtures and refractory materials can be formed in space by cosmic ion irradiation. This finding has been recently confirmed by the Stardust mission, which revealed in some of the cometary particles collected in space and returned to earth carbonaceous materials that have been processed by cosmic ion irradiation. Copyright © 2008 John Wiley & Sons, Ltd.

We present the results of UV irradiation with Lyα photons of carbon grains with a water ice cap at 11 K. Formation of CO and CO2 molecules takes place during irradiation. An estimation of the formation cross section of these molecules by Lyα photons has been obtained from the intensity increase of their infrared stretching bands as a function of the photon fluence. The fraction of carbon in the grains converted to CO and CO2 by UV photons is 0.06 and 0.05, respectively. The spectral profile of the CO stretching feature and that of the CO2 bending mode indicate a polar environment for these molecules. On the basis of the present laboratory results and those obtained in previous work on ion irradiation of similar samples, it has been possible to estimate the contribution of polar CO and CO2 produced on carbon grains by energetic processing to the observed column densities of these molecules for dense clouds whose visual extinction is known. A significant amount of polar CO and CO2 is produced through the mechanism we have studied. Furthermore, we have found that the laboratory profile of the bending band of CO2 produced on carbon grains is compatible with that observed toward the field star Elias 16.

We have studied the synthesis of carbon dioxide from solid carbon monoxide at 16 K induced by photolysis with Lyman-α photons and by irradiation with 200 keV protons to quantitatively compare the effects of photolysis and ion irradiation on CO ice and to determine the importance of these processes in interstellar ice grains. The CO and CO2 concentrations during irradiation of an initially pure CO film evolve with fluence to a saturation value, a behaviour that is explained by a two-state model. Our results indicate that the initial CO2 production rates for both radiation processes are similar when normalized to the absorbed energy and that the solid CO2 abundance observed in the interstellar ices cannot be explained only by radiolysis and photolysis of pure solid CO.

We present the results of experiments aimed at studying the influence of the type of grain on the chemical composition of the ice mantles during energetic processing under simulated dense medium conditions. Formation of CO and CO2 molecules occurs when hydrogenated carbon grains with a water ice cap are irradiated with 30 keV He+ ions at low temperature. The fraction of carbon in the grains converted to CO and CO2 by ions is at least 0.03 and 0.02, respectively. An estimation of the formation cross section of these molecules by 30 keV He+ ions has been derived from the intensity increase of their infrared stretching bands as a function of the ion fluence. On the basis of the laboratory results, it has been possible to evaluate the contribution of CO and CO2 produced on carbon grain by cosmic rays to the observed column densities of these molecules for dense clouds whose visual extinction is known. The mechanism we have studied does not dominate other CO2 formation processes; however, its contribution is in addition to other processes occurring on ice mantles. The spectral profile and the contribution to the observed column densities make solid CO formed by cosmic-ray irradiation of ice-layered carbon grains a good candidate for the red component of the interstellar CO stretching feature, which is generally attributed to CO mixed in with water ice. As a consequence of the formation of CO and CO2 molecules on carbon grains, a slow chemical erosion of the particles takes place.

Using infrared and Raman spectroscopies, we have studied the effects induced by ion irradiation on icy mixtures at low temperature (T=12 K) and after warm up to room temperature. In particular, we have considered mixtures made of H2O, CO, CH4, and N2. These mixtures have been irradiated with 30 keV He+ and 60 keV Ar2+ ions. After ion irradiation at low temperature, several new absorption features appear in the infrared spectra, some of which may be due to N-bearing molecular species. A refractory organic residue is left over after warm-up to room temperature. After further irradiation of the residue at room temperature, the intensity of all infrared absorption features decreases. Raman spectroscopy of similar mixtures has shown that ion irradiation causes a modification of the structure of the samples which evolve towards an amorphous carbon.

Context. It has been confirmed that solid carbon dioxide (CO2) is abundantly present along the line of sight to quiescent clouds and star-forming regions via space IR observations with ISO-SWS and Spitzer Space Telescope. Since CO2 has low abundance in the gas-phase, the assumption is that it is synthesized on grains after energetic processing of icy mantles and surface reactions. Aims: The role of solid carbon is investigated as a reservoir for molecule formation and structural modifications of the material with and without an ice layer upon ion bombardment. Methods: A gas-phase condensation technique was used to prepare a layer of 13C amorphous grains. These grains were covered with H2O and O2 ice and finally bombarded with 200 keV protons. The formation of new molecular species was analyzed using IR spectroscopy. The formation cross sections of solid 13CO and 13CO2 were determined from the increase in the column density as a function of the fluence. In addition, bare carbon grains were bombarded with a comparable fluence of protons to study the processing of the grains without ice layer. Imaging techniques such as transmission electron microscopy were used to monitor the changes in the structure. Results: CO and CO2 were formed efficiently at the interface between ice and solid carbon grains at the expense of solid carbon, leading to strong grain erosion. Given the initial thickness of our C-samples (about 120 nm), this resulted in an erosion of about 50% after 200 keV proton bombardment with 6.76 × 1016 ions/cm2. The column density of CO and CO2 follows an exponential trend as a function of the irradiation fluence. The asymptotic values obtained when O2 ice is deposited on top of the carbon grains are about one order of magnitude higher than the values obtained when H2O ice is deposited on the solid carbon layer. The carbon grains were strongly graphitized upon ion bombardment in a surface layer. Less graphitization accompanied by the formation of fullerene molecules and structures from cage fragments present in the original material were observed beneath the graphitic layer. Conclusions: The formation of CO and CO2 at the expense of solid carbon strongly restricts the lifetime of the solid carbon material and may influence the formation of more complex molecules in astrophysical environments. Graphitization of carbonaceous grains upon ion bombardment affect the spectral properties of the carbon grains in particular in the far-IR range.

We have studied by infrared absorption spectroscopy the effects induced by fast ions (30 keV) and Lyman-α photons (10.2 eV) on some molecular ices at low temperature (10–20 K). It is well known that in both cases the physical and chemical properties of the ices are modified. However while the energy released by ions depends mainly on their energy and on the target species, the effects induced by photons also depend on the optical properties of the sample. Here we show that the effects of ion irradiation and UV photolysis are comparable on fresh ices (i.e. at low doses) but are increasingly different as processing is continued (i.e. at high doses).

Context. Carbon dioxide (CO2) is one of the most abundant species detected in icy grain mantles in star forming regions. Laboratory experiments have shown that CO2 molecules are efficiently formed in the solid state under interstellar conditions. Specifically, solid CO2 can be formed through energetic (e.g. UV photolysis, electron and ion bombardment) and non-energetic mechanisms (atom-addition reactions). Aims: Here we investigate the role of low-energy cosmic-ray bombardment in the formation of solid CO2 in quiescent dense molecular clouds. Methods: We performed laboratory experiments to study the formation of CO2 after ion irradiation with 200 keV H+ of astrophysical relevant ice mixtures. Laboratory spectra are used to fit the profile of the CO2 bending mode band observed at about 15.2 μm (660 cm-1) by the Spitzer Space Telescope in the line of sight to background sources. Results: From a qualitative point of view, good fits to observations are obtained by considering either three or four laboratory components. From a quantitative point of view, a better result is obtained with four components, i.e. when a spectrum of CO2 formed after ion irradiation of CH3OH ice is added to the fitting procedure. Conclusions: Our results support the hypothesis that energetic processing of icy grain mantles is an efficient formation mechanism of CO2 ice also in quiescent dark cloud regions, and indirectly suggest the presence of CH3OH in icy grain mantles in interstellar cold regions.

In the last 20 years we have studied some effects induced by fast ions (E approximately keV-MeV) impinging on solid materials (mainly ices) with a view to their astrophysical relevance. The main techniques used have been infrared and Raman spectroscopy. Here we review some of the results obtained so far concerning, in particular, the formation of new species not present in the original sample. When hydrocarbons are an important constituent of the target ion irradiation gives rise also to a refractory residue which is left over after warming up. In addition we present some preliminary results of a new study, still in progress, on the infrared properties of the organic residue formed after irradiation of an icy mixture with H-, C-, N- and O-bearing species. Furthermore we present the micro-Raman spectra of some fragments of Orgueil a carbonaceous chondrite meteorite. Some astrophysical applications of these laboratory results are also discussed.

We have investigated the effects induced by ion bombardment of mixtures containing nitrogen-bearing compounds at low temperatures. The results show the formation of a band at 2080 cm-1 in binary mixtures, NH3:CH4 and N2:CH4, which we attribute to HCN embedded in the organic residue formed by ion irradiation. In addition to this band, ternary mixtures containing an oxygen-bearing species (i.e., H2O) form a compound with a prominent absorption band at about 2165 cm-1 (4.62 microns). We ascribe this band to a nitrile compound containing O that is bonded to the organic residue. A detailed comparison of the laboratory results with astronomical data of the 4.62 microns absorption band in protostellar spectra shows good agreement in peak position and profile. Our experimental studies show that N2, which is a more likely interstellar ice component than NH3, can be the molecular progenitor of the carrier of the interstellar band. This is an alternative to the pathway by which UV photolysis of NH3-containing ices produces the 4.62 microns band and implies that ion bombardment may well play an important role in the evolution of interstellar ices. Here, we discuss the implications of our studies for the chemical route by which the carrier of the 4.62 microns band is formed in these laboratory experiments.

Space missions, as EChO, or ground based experiments, as SPHERE, have been proposed to measure the atmospheric transmission, reflection and emission spectra. In particular, EChO is foreseen to probe exoplanetary atmospheres over a wavelength range from 0.4 to 16 micron by measuring the combined spectra of the star, its transmission through the planet atmosphere and the emission of the planet. The planet atmosphere characteristics and possible biosignatures will be inferred by studying such composite spectrum in order to identify the emission/absorption lines/bands from atmospheric molecules such as water (H2O), carbon monoxide (CO), methane (CH4), ammonia (NH3) etc. The interpretation of the future EChO observations depends upon the understanding of how the planet atmosphere affects the stellar spectrum and how this last affects the planet emission/absorption. In particular, it is important to know in detail the optical characteristics of gases in the typical physical conditions of the planetary atmospheres and how those characteristics could be affected by radiation induced phenomena such as photochemical and biological one. Insights in this direction can be achieved from laboratory studies of simulated planetary atmosphere of different pressure and temperature conditions under the effects of radiation sources, used as proxies of different bands of the stellar emission.

We present selected results of a series of experiments, performed in our laboratory, on the implantation of ⋍ 1 keV/amu reactive (H, C, N, O) and unreactive (He, Ar) ions into silicon, silicates and frozen gases. The purpose to irradiate the last two samples, is to simulate solar wind ion implantation on planetary objects. In particular we investigated on the possibility of producing chemical bonds between the projectile and the target atoms searching for the appearance of characteristic IR bands. When the impinging ion is reactive (H, C, N, O) we found several cases of newly produced molecular species that include the projectile.

We report recent experimental studies on the physical—chemical effects induced by fast ions colliding with frozen gases (CO. CH3OH, CH4, CO2) and mixtures with water simulating icy targets in space (frosts on external planets and satellites. comets and interstellar ices). We have studied, by lR spectroscopy, the formation of new molecules. the alteration of band profile. the spectral changes of the original compounds and the formation of an organic refractory residue left over after ion irradiation. In particular; we present here the results of the measurements of the CO CO2 ratio resulting from the irradiation of several ice mixtures.

Context. Knowledge about the composition and structure of interstellar ices is mainly based on the comparison between astronomical and laboratory spectra of astrophysical ice analogues. Carbon monoxide is one of the main components of the icy mantles of dust grains in the interstellar medium. Because of its relevance, several authors have studied the spectral properties of solid CO both pure and in mixtures. Aims: The aim of this work is to study the profile (shape, width, peak position) of the solid CO band centered at about 2140 cm-1 at low temperature, during warm up, and after ion irradiation to search for a structural variation of the ice sample. We also report on the appearance of the longitudinal optical-transverse optical (LO-TO) splitting in the infrared spectra of CO films to understand if this phenomenon can be related to a phase change. Methods: We studied the profile of the 2140 cm-1 band of solid CO by means of infrared and Raman spectroscopy. We used a free web interface that we developed that allows us to calculate the refractive index of the sample to measure the thickness of the film. Results: The profile of the fundamental band of solid CO obtained with infrared and Raman spectroscopy does not show any relevant modification after warm up or ion bombardment in the dose range investigated. We explain that the LO-TO splitting is not connected to a structural variation of the film. Ion irradiation causes the formation of new molecular species. Raman spectroscopy allowed us to detect, among other bands, a band centered at 1817 cm-1 that has been attributed to the infrared inactive species C2 and a band centered at 1767 cm-1 that remains unidentified.

Water ice in the outer solar system can either have condensed from the gas phase or have been brought in by colliding bodies, such as interplanetary ice grains to comets. Since icy bodies lack a protective atmosphere, their surface is subject to irradiation by photons, ions and electrons. This chapter discusses how energetic radiation affects the physical and chemical properties of a pure water ice surface, and how the outcome of radiation processes depends on the properties of the surface and on the environment (atmosphere, particle flux and energies).

Our groups in Brazil, France and Italy have been active, among others in the world, in performing experiments on physical-chemical effects induced by fast ions colliding with solids (frozen gases, carbonaceous and organic materials, silicates, etc.) of astrophysical interest. The used ions span a very large range of energies, from a few keV to hundreds MeV. Here we present a summary of the results obtained so far on the formation of oxidants (hydrogen peroxide and ozone) after ion irradiation of frozen water, carbon dioxide and their mixtures. Irradiation of pure water ice produces hydrogen peroxide whatever is the used ion and at different temperatures. Irradiation of carbon dioxide and water frozen mixtures result in the production of molecules among which hydrogen peroxide and ozone. The experimental results are discussed in the light of the relevance they have to support the presence of an energy source for biosphere on Europa and other icy moons in the outer Solar System., This research has been supported by the European COST Action CM0805: The Chemical Cosmos.

We report new results from recent experimental studies on physico-chemical effects induced in frozen gases and mixtures (CO, CO2, CH4, H2O and SO2) simulating ice targets in space (frosts on external planets and satellites, and comets). In particular we have studied, by UV-Vis-IR spectroscopy, the formation of new molecules, the alteration of band profiles and the spectral behavior of the original compounds. The ratio CO/CO2 has been measured, as a function of ion fluence, in several frozen gases (or mixtures). These results are discussed in the light of their relevance in some planetary environments. In particular, we suggest that ion irradiation, which is especially intense at Io, can modify the spectral properties of frozen SO2 thus contributing to explain the spectral behavior of this Jovian moon. The production, by cosmic ion irradiation, of CO and CO2 at the surfaces and/or in the atmospheres of Titan, Triton, Pluto and Charou is discussed. Some predictions of the expected CO/CO2 ratio at the surfaces and/or in the atmospheres of those objects are provided.

We have studied some of the most important characteristics of frozen methane with a view to their astrophysical relevance. We have measured its density at low temperature (10 – 20 K) and its IR spectrum has been studied in order to measure the integrated absorbances of the most intense absorption bands. Methane bearing icy grain mantles in the interstellar medium and methane-rich surfaces on planetary objects are continuously processed by energetic ions and UV photons, thus we have also studied in laboratory the effects of ion irradiation on methane ice.

Context. Solid interstellar CO_2 is an abundant component of ice dust mantles. Its ubiquity towards quiescent molecular clouds, as well as protostellar envelopes, has recently been confirmed by the IRS (InfraRed Spectrograph) aboard the Spitzer Space Telescope. Although it has been shown that CO_2 cannot be efficiently formed in the gas phase, the CO_2 surface formation pathway is still unclear. To date several CO_2 surface formation mechanisms induced by energetic (e.g., UV photolysis and cosmic ray irradiation) and non-energetic (e.g., cold atom addition) input have been proposed. Aims. Our aim is to investigate the contribution of cosmic ray irradiation to the formation of CO_2 in different regions of the interstellar medium (ISM). To achieve this goal we compared quantitatively laboratory data with the CO_2 bending mode band profile observed towards several young stellar objects (YSOs) and a field star by the Spitzer Space Telescope. Methods. All the experiments presented here were performed at the Laboratory for Experimental Astrophysics in Catania (Italy). The interstellar relevant samples were all irradiated with fast ions (30−200 keV) and subsequently annealed in a stainless steel high vacuum chamber (P < 10^(-7) mbar). Chemical and structural modifications of the ice samples were monitored by means of infrared spectroscopy. Laboratory spectra were then used to fit some thirty observational spectra. Results. A qualitative analysis shows that a good fit can be obtained with a minimum of two components. The choice of the laboratory components is based on the chemical-physical condition of each source. A quantitative analysis of the sources with known visual extinction (A_V) and methanol abundances highlights that the solid carbon dioxide can be efficiently and abundantly formed after ion irradiation of interstellar ices in all the selected YSOs in a time compatible with cloud lifetimes (3 × 10^7 years). Only in the case of field stars can the expected CO_2 column density formed upon energetic input not explain the observed abundances. This result, to be confirmed along the line of sight to different quiescent clouds, gives an indirect indication that CO_2 can also be formed in an early cloud stage through surface reactions induced by non-energetic mechanisms. In a later stage, when ices are exposed to higher UV and cosmic ray doses, the CO_2 total abundance is strongly affected by energetic formation mechanisms. Conclusions. Our results indicate that energetic processing of icy grain mantles significantly contribute to the formation of solid phase interstellar CO_2.

Ices, silicates and carbonaceous materials have been detected in several astrophysical environments such as interstellar molecular clouds, comets, and planetary surfaces. These solids are continuously exposed to ion irradiation and UV photolysis. Our knowledge on the properties of solids and molecules and on the modification induced by fast ions (keV-MeV) and UV photons is mainly based on laboratory experiments and on the comparison of experimental results with observations. Here we will give a few examples of the role of laboratory experiments to our understanding of the physical and chemical properties of ices in space.

We present the results of recent experiments on some physico-chemical effects induced by fast ion colliding with solids of relevance for the physics of planetary objects. The production of molecular solids, polymerlike materials and amorphous carbon by irradiation of frozen hydrocarbons and pentacene is discussed. We also report on a set of experimental results obtained irradiating methanol and water-methanol mixtures. Because of bombardment different species form. The techniques used for the analysis are “in situ” infrared (IR) and Raman spectroscopy. The experimental results are finally discussed in the light of their relevance for planetary physics.