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Interstellar and cometary ices play an important role in the formation of planetary systems around young stars. Their main constituent is amorphous solid water (ASW). Although ASW is widely studied, vibrational energy dissipation and structural changes due to vibrational excitation are less well understood. The hydrogen-bonding network is likely a crucial component in this. Here we present experimental results on hydrogen-bonding changes in ASW induced by the intense, nearly monochromatic mid-IR free-electron laser (FEL) radiation of the FELIX-2 beamline at the HFML-FELIX facility at the Radboud University in Nijmegen, the Netherlands. Structural changes in ASW are monitored by reflection-absorption infrared spectroscopy and depend on the irradiation history of the ice. The experiments show that FEL irradiation can induce changes in the local neighborhood of the excited molecules due to energy transfer. Molecular Dynamics simulations confirm this picture: vibrationally excited molecules can reorient for a more optimal tetrahedral surrounding without breaking existing hydrogen bonds. The vibrational energy can transfer through the hydrogen-bonding network to water molecules that have the same vibrational frequency. We hence expect a reduced energy dissipation in amorphous material with respect to crystalline material due to the inhomogeneity in vibrational frequencies as well as the presence of specific hydrogen-bonding defect sites which can also hamper the energy transfer., 34 page, 9 figures

Interstellar ice grains are believed to play a key role in the formation of many of the simple and complex organic species detected in space. However, many fundamental questions on the physicochemical processes linked to the formation and survival of species in ice grains remain unanswered. Field work at large-scale facilities such as free-electron lasers (FELs) can aid the investigation of the composition and morphology of ice grains by providing novel tools to the laboratory astrophysics community. We combined the high tunability, wide infrared spectral range and intensity of the FEL beam line FELIX-2 at the HFML-FELIX Laboratory in the Netherlands with the characteristics of the ultrahigh vacuum LISA end station to perform wavelength-dependent mid-IR irradiation experiments of space-relevant pure carbon dioxide (CO2) ice at 20 K. We used the intense monochromatic radiation of FELIX to inject vibrational energy at selected frequencies into the CO2 ice to study ice restructuring effects in situ by Fourier Transform Reflection-Absorption Infrared (FT-RAIR) spectroscopy. This work improves our understanding of how vibrational energy introduced by external triggers such as photons, electrons, cosmic rays, and thermal heating coming from a nascent protostar or field stars is dissipated in an interstellar icy dust grain in space. Moreover, it adds to the current literature debate concerning the amorphous and polycrystalline structure of CO2 ice observed upon deposition at low temperatures, showing that, under our experimental conditions, CO2 ice presents amorphous characteristics when deposited at 20 K and is unambiguously crystalline if deposited at 75 K., Comment: Published in the 'Journal of Molecular Spectroscopy'. Includes 11 pages, 7 figures

Laboratory experiments have confirmed that the radiolytic decay rate of astrochemical ice analogues is dependent upon the solid phase of the target ice, with some crystalline molecular ices being more radio-resistant than their amorphous counterparts. The degree of radio-resistance exhibited by crystalline ice phases is dependent upon the nature, strength, and extent of the intermolecular interactions that characterise their solid structure. For example, it has been shown that crystalline CH3OH decays at a significantly slower rate when irradiated by 2 keV electrons at 20 K than does the amorphous phase due to the stabilising effect imparted by the presence of an extensive array of strong hydrogen bonds. These results have important consequences for the astrochemistry of interstellar ices and outer Solar System bodies, as they imply that the chemical products arising from the irradiation of amorphous ices (which may include prebiotic molecules relevant to biology) should be more abundant than those arising from similar irradiations of crystalline phases. In this present study, we have extended our work on this subject by performing comparative energetic electron irradiations of the amorphous and crystalline phases of the sulphur-bearing molecules H2S and SO2 at 20 K. We have found evidence for phase-dependent chemistry in both these species, with the radiation-induced exponential decay of amorphous H2S being more rapid than that of the crystalline phase, similar to the effect that has been previously observed for CH3OH. For SO2, two fluence regimes are apparent: a low-fluence regime in which the crystalline ice exhibits a rapid exponential decay while the amorphous ice possibly resists decay, and a high-fluence regime in which both phases undergo slow exponential-like decays., Comment: Published in Frontiers in Chemistry (open access)

The detection of ozone (O

The detection of ozone (O3) in the surface ices of Ganymede, Jupiters largest moon, and of the Saturnian moons Rhea and Dione, has motivated several studies on the route of formation of this species. Previous studies have successfully quantified trends in the production of O3 as a result of the irradiation of pure molecular ices using ultraviolet photons and charged particles (i.e., ions and electrons), such as the abundances of O3 formed after irradiation at different temperatures or using different charged particles. In this study, we extend such results by quantifying the abundance of O3 as a result of the 1 keV electron irradiation of a series of 14 stoichiometrically distinct CO2:O2 astrophysical ice analogues at 20 K. By using mid-infrared spectroscopy as our primary analytical tool, we have also been able to perform a spectral analysis of the asymmetric stretching mode of solid O3 and the variation in its observed shape and profile among the investigated ice mixtures. Our results are important in the context of better understanding the surface composition and chemistry of icy outer Solar System objects, and may thus be of use to future interplanetary space missions such as the ESA Jupiter Icy Moons Explorer and the NASA Europa Clipper missions, as well as the recently launched NASA James Webb Space Telescope., Accepted for publication in Phys. Chem. Chem. Phys

Many experimental parameters determine the chemical and physical properties of interstellar ice analogues, each of which may influence the molecular synthesis that occurs in such ices. In part 1, James et al., RSC Adv., 2020, 10, 37517, we demonstrated the effects that the stoichiometric mixing ratio had on the chemical and physical properties of CO2 : NH3 mixtures and the impact on molecular synthesis induced by thermal processing. Here, in part 2, we extend this to include 1 keV electron irradiation at 20 K of several stoichiometric mixing ratios of CO2 : NH3 ices followed by thermal processing. We demonstrate that not all stoichiometric mixing ratios of CO2 : NH3 ice form the same products. Not only did the 4 : 1 ratio form a different residue after thermal processing, but O3 was observed after electron irradiation at 20 K, which was not observed in the other ratios. For the other ratios, the residue formed from a thermal reaction similar to the work shown in Part 1. However, conversion of ammonium carbamate to carbamic acid was hindered due to electron irradiation at 20 K. Our results demonstrate the need to systematically investigate stoichiometric mixing ratios to better characterise the chemical and physical properties of interstellar ice analogues to further our understanding of the routes of molecular synthesis under different astrochemical conditions.

The detection of the amino acid glycine and its amine precursor methylamine on the comet 67P/Churyumov-Gerasimenko by the Rosetta mission provides strong evidence for a cosmic origin of prebiotics on Earth. How and when such complex organic molecules form along the process of star- and planet-formation remains debated. We report the first laboratory detection of glycine formed in the solid phase through atom and radical-radical addition surface reactions under cold dense interstellar cloud conditions. Our experiments, supported by astrochemical models, suggest that glycine forms without the need for energetic irradiation, such as UV photons and cosmic rays, in interstellar water-rich ices, where it remains preserved, in a much earlier star-formation stage than previously assumed. We also confirm that solid methylamine is an important side-reaction product. A prestellar formation of glycine on ice grains provides the basis for a complex and ubiquitous prebiotic chemistry in space enriching the chemical content of planet-forming material., Preprint of the original submitted version

Water (H2O) ice is ubiquitous component of the universe, having been detected in a variety of interstellar and Solar System environments where radiation plays an important role in its physico-chemical transformations. Although the radiation chemistry of H2O astrophysical ice analogues has been well studied, direct and systematic comparisons of different solid phases are scarce and are typically limited to just two phases. In this article, we describe the results of an in-depth study of the 2 keV electron irradiation of amorphous solid water (ASW), restrained amorphous ice (RAI) and the cubic (Ic) and hexagonal (Ih) crystalline phases at 20 K so as to further uncover any potential dependence of the radiation physics and chemistry on the solid phase of the ice. Mid-infrared spectroscopic analysis of the four investigated H2O ice phases revealed that electron irradiation of the RAI, Ic, and Ih phases resulted in their amorphization (with the latter undergoing the process more slowly) while ASW underwent compaction. The abundance of hydrogen peroxide (H2O2) produced as a result of the irradiation was also found to vary between phases, with yields being highest in irradiated ASW. This observation is the cumulative result of several factors including the increased porosity and quantity of lattice defects in ASW, as well as its less extensive hydrogen-bonding network. Our results have astrophysical implications, particularly with regards to H2O-rich icy interstellar and Solar System bodies exposed to both radiation fields and temperature gradients., Published in the European Physical Journal D: Atomic, Molecular, Optical, and Plasma Physics

Amorphous solid water (ASW) is one of the most widely studied solid phase systems. A better understanding of the nature of inter- and intramolecular forces in ASW is, however, still required to correctly interpret the catalytic role of ASW in the formation and preservation of molecular species in environments such as the icy surfaces of Solar System objects, on interstellar icy dust grains and potentially even in the upper layers of the Earth's atmosphere. In this work, we have systematically exposed porous ASW (pASW) to mid-infrared radiation generated by a free-electron laser at the HFML-FELIX facility in the Netherlands to study the effect of vibrational energy injection into the surface and bulk modes of pASW. During multiple sequential irradiations on the same ice spot, we observed selective effects both at the surface and in the bulk of the ice. Although the density of states in pASW should allow for a fast vibrational relaxation through the H-bonded network, part of the injected energy is converted into structural ice changes as illustrated by the observation of spectral modifications when performing Fourier transform infrared spectroscopy in reflection-absorption mode. Future studies will include the quantification of such effects by systematically investigating ice thickness, ice morphology, and ice composition., Published in The Journal of Physical Chemistry A

Methoxymethanol (CH3OCH2OH, MM) has been identified through gas-phase signatures in both high- and low-mass star-forming regions. This molecule is expected to form upon hydrogen addition and abstraction reactions in CO-rich ice through radical recombination of CO hydrogenation products. The goal of this work is to investigate experimentally and theoretically the most likely solid-state MM reaction channel -- the recombination of CH2OH and CH3O radicals -- for dark interstellar cloud conditions and to compare the formation efficiency with that of other species that were shown to form along the CO-hydrogenation line. Hydrogen atoms and CO or H2CO molecules are co-deposited on top of the predeposited H2O ice to mimic the conditions associated with the beginning of 'rapid' CO freeze-out. Quadrupole mass spectrometry is used to analyze the gas-phase COM composition following a temperature programmed desorption. Monte Carlo simulations are used for an astrochemical model comparing the MM formation efficiency with that of other COMs. Unambiguous detection of newly formed MM has been possible both in CO+H and H2CO+H experiments. The resulting abundance of MM with respect to CH3OH is about 0.05, which is about 6 times less than the value observed toward NGC 6334I and about 3 times less than the value reported for IRAS 16293B. The results of astrochemical simulations predict a similar value for the MM abundance with respect to CH3OH factors ranging between 0.06 to 0.03. We find that MM is formed by co-deposition of CO and H2CO with H atoms through the recombination of CH2OH and CH3O radicals. In both the experimental and modeling studies, the efficiency of this channel alone is not sufficient to explain the observed abundance of MM. These results indicate an incomplete knowledge of the reaction network or the presence of alternative solid-state or gas-phase formation mechanisms., Comment: 8 pages, 8 figures

The successive addition of H atoms to CO in the solid phase has been hitherto regarded as the primary route to form methanol in dark molecular clouds. However, recent Monte Carlo simulations of interstellar ices alternatively suggested the radical-molecule H-atom abstraction reaction CH3O + H2CO -> CH3OH + HCO, in addition to CH3O + H -> CH3OH, as a very promising and possibly dominating (70 - 90 %) final step to form CH3OH in those environments. Here, we compare the contributions of these two steps leading to methanol by experimentally investigating hydrogenation reactions on H2CO and D2CO ices, which ensures comparable starting points between the two scenarios. The experiments are performed under ultrahigh vacuum conditions and astronomically relevant temperatures, with H:H2CO (or D2CO) flux ratios of 10:1 and 30:1. The radical-molecule route in the partially deuterated scenario, CHD2O + D2CO -> CHD2OD + DCO, is significantly hampered by the isotope effect in the D-abstraction process, and can thus be used as an artifice to probe the efficiency of this step. We observe a significantly smaller yield of D2CO + H products in comparison to H2CO + H, implying that the CH3O-induced abstraction route must play an important role in the formation of methanol in interstellar ices. Reflection-Absorption InfraRed Spectroscopy (RAIRS) and Temperature Programmed Desorption-Quadrupole Mass Spectrometry (TPD-QMS) analyses are used to quantify the species in the ice. Both analytical techniques indicate constant contributions of ~80 % for the abstraction route in the 10 - 16 K interval, which agrees well with the Monte Carlo conclusions. Additional H2CO + D experiments confirm these conclusions., Comment: 10 pages, 1 table, 6 figures. Accepted in the Astrophysical Journal Letters

Laboratory studies of the radiation chemistry occurring in astrophysical ices have sought to better understand the dependence of this chemistry on a number of experimental parameters, such as the temperature of the ice or the energy of the incident radiation. One experimental parameter which has received significantly less attention from the research community is that of the phase of the solid ice under investigation. Our research group based at the Institute for Nuclear Research (Atomki) in Debrecen, Hungary has therefore made use of the custom-built Ice Chamber for Astrophysics-Astrochemistry (ICA) [1,2] to conduct experiments aimed at providing a better understanding of the role of the solid phase of an ice in determining the outcome of its radiation (astro)chemistry. We have performed a series of systematic and comparative 2 keV electron irradiations of the amorphous and crystalline phases of various pure astrophysical ice analogues, including N2O, CH3OH, and H2O, at 20 K [3,4]. The radiation-induced decay of these ices and the concomitant formation of products were monitored in situ using FT-IR spectroscopy. A direct comparison between the irradiated amorphous and crystalline CH3OH ices revealed a significantly more rapid decay of the former compared to the latter. Interestingly, a significantly smaller difference was observed when comparing the decay rates of the amorphous and crystalline N2O ices (Figure 1). The extent of the similarity between the radiolytic decay curves of the amorphous and crystalline phases of these ices has been quantified by applying the weighted Jaccard coefficient, Jw (also sometimes referred to as the Tanimoto coefficient). This coefficient measures the similarity between two real, non-zero functions and varies between 0-1, with the 0 indicating no statistical similarity whatsoever and the 1 indicating identical functions. In the case of the radiolytic decay curves for the amorphous and crystalline CH3OH ices, Jw = 0.40, while in the case of the investigated N2O ices this was much higher at Jw = 0.80. Figure 1: Electron-induced decay of CH3OH (above) and N2O (below) ice phases with increasing 2 keV electron fluence. Reproduced from Mifsud et al. (2022) with permission of the Royal Society of Chemistry [3]. These results have been interpreted in terms of the strength and extent of the intermolecular forces of attraction present in each molecular ice. The strong and extensive hydrogen-bonding network that exists in the crystalline CH3OH – but not in the amorphous phase – is thought to add a significant stabilizing effect to this phase which makes it more resistant to radiation-induced decay. On the other hand, although the alignment of the molecular dipole of N2O is expected to be more extensive in the crystalline phase, its weak attractive potential does not significantly stabilize the crystalline phase against radiation-induced decay compared to the amorphous phase as in the case of CH3OH. Experiments were also performed on various phases of H2O ices using 2 keV electrons. Irradiated amorphous solid water (ASW), restrained amorphous ice (RAI), cubic crystalline ice (Ic), and cubic hexagonal ice (Ih) were found to demonstrate different responses upon the onset of electron irradiation (Figure 2). For example, the compaction of ASW ice was noted to occur fairly quickly. The ordered phases, on the other hand, all underwent amorphization as a result of their irradiation by energetic electrons. Interestingly, the amorphization of Ih was noted to require a higher electron fluence compared to those of RAI and Ic (Figure 3). This is perhaps not unexpected, as these latter phases are only meta-stable with respect to Ih. Figure 2: FTIR spectra of ASW, RAI, Ic, and Ih ice phases before and after irradiation using a fluence of 1.3×1017 electrons cm–2. Reproduced from Mifsud et al. (2022) with kind permission of The European Physical Journal [4]. Large variations in the appearance and shape of the mid-infrared absorption bands between the crystalline and amorphous H2O ices made the use of the weighted Jaccard coefficient difficult and inappropriate. As such, the difference in the radiolytic decay rates of these ices was gauged indirectly by measuring the yield of H2O2 observed after electron irradiation of each phase. The ASW ice was found to be the most chemically productive in this way, with 0.32% of the H2O being converted to H2O2. On moving to more ordered phases, however, the H2O2 yield was found to progressively decline, with 0.21, 0.16, and 0.14% of the H2O being converted to H2O2 as a result of the irradiation of the RAI, Ic, and Ih phases, respectively. Our results have important implications for radiative astrochemistry of interstellar and outer Solar System ices, as it is clear that the radiolytic decay and, by extension, the potential chemical productivities of these ices are greater when they are in the amorphous state rather than the crystalline phase. Given that most astrophysical ices undergo cycles of thermally induced crystallization and space radiation induced amorphization, our results suggest that the formation of new molecules (including those complex molecules of relevance to biology and the emergence of life) as a result of the processing of these ices by galactic cosmic rays, the solar wind, or giant planetary magnetospheric plasmas is most productive in those astrophysical regions where the amorphization process is more efficient. This is not an unreasonable conclusion, particularly in light of the recent spate of discoveries of complex organic molecules in the pre-stellar cloud TMC-1 [e.g., 5,6]. Figure 3: Structured H2O stretching modes were observed to broaden as a result of electron-induced amorphization of the ices; which is suggested to be slower in the Ih phase. The authors all gratefully acknowledge funding from the Europlanet 2024 RI which has been funded by the European Union Horizon 2020 Research Innovation Programme under grant agreement No. 871149. References:[1] P. Herczku, et al. Rev. Sci. Instrum. 92, 084501 (2021) [2] D.V. Mifsud, et al. Eur. Phys. J. D. 75, 182 (2021) [3] D.V. Mifsud, et al. Phys. Chem. Chem. Phys. 24, 10974 (2022) [4] D.V. Mifsud, et al. Eur. Phys. J. D. 76, 87 (2022) [5] B.A. McGuire et al. Science 371, 1265 (2021) [6] K.L.K. Lee et al. Astrophys. J. Lett. 908, L11 (2021)

Ices are widely present in the cold regions across the Universe, for instance, in the interstellar medium as mantles on interstellar and circumstellar dust and on the surfaces of small bodies of the Solar System - beyond the distance around 3-5 AU known as the “snowline" (i.e. at temperatures below 150-170 K). The continuous energetic processing of icy objects in the Solar System induces physical and chemical changes within the ice. Laboratory experiments that simulate energetic processing (ions, photons, and electrons) of ices are therefore essential for interpreting and directing future astronomical observations. Here we provide vacuum ultraviolet (VUV) and UV-Vis photoabsorption spectroscopic data of pristine and energetically processed (electron irradiated) space-related ices. Experiments were performed using a custom-made Portable Astrochemistry Chamber (PAC), which has a base pressure of 10-9 mbar. Photoabsorption spectra of ices were measured at the AU-UV beam line of the ASTRID2 synchrotron light source at Aarhus University in Denmark (see Eden et al. 2006; Palmer et al. 2015). We present the results of three series of experiments: one dedicated to the study of nitrogen- and oxygen-rich ices (Ioppolo et al., 2020); the other one to the spectroscopic study of carbonic acid as formed and destroyed under conditions relevant to space (Ioppolo et al., 2021); and the third one to the study of photoabsorption spectra of O2 ice, both pure and mixed with other species (Migliorini et al, 2021). Results are discussed in light of their relevance to various astrophysical environments, e.g., the icy moons of Saturn and Jupiter. Laboratory VUV-UV-vis spectra of ices can help their future identification on the surface of icy objects in the Solar System by the upcoming Jupiter ICy moons Explorer mission and on interstellar dust by the James Webb Space Telescope spacecraft. This research was partly supported by the Italian Space Agency (Grant ASI-INAF n. 2018-25-HH-0). REFERENCES: Eden, S., Limão-Vieira, P., Hoffmann, S. V., & Mason, N. J. 2006, Chem. Phys., 323, 313 Ioppolo, S., Kanuchova Z., James, R.L., Dawes, A., Jones, N.C., Hoffmann, S.V., Mason, N.J., Strazzulla, G. 2020, Astron. Astrophys. 641, A154 Ioppolo, S., Kanuchova Z., James, R.L., Dawes, A., Ryabov, A., Dezalay, J., Jones, N.C., Hoffmann, S.V., Mason, N.J., Strazzulla, G. 2021, Astron. Astrophys. 645, A172 Migliorini, A., Kanuchova Z., Ioppolo, S., Jones, N.C., Hoffmann, S.V., Tosi, F., Piccioni, G., Barbieri, M. 2021, Icarus, submitted Palmer, M. H., Ridley, T., Hoffmann, S. V., et al. 2015, J. Chem. Phys., 142, 134302

The Universe is molecular in nature, as over 200 molecules have been detected in the gas-phase in the interstellar and circumstellar medium (ISM/CSM). Starting from molecular hydrogen, many species including H2O, CO2, NH3, CH4, CH3OH, and other complex organic molecules (COMs) have been shown to be formed efficiently on the surface of interstellar ice grains throughout the star-formation process. Interstellar ices are believed to be the main carriers of prebiotic molecules that have been included in the outer Solar System’s ice objects such as moons, comets, and Kuiper Belt Objects (KBOs). Therefore, understanding how COMs form and evolve in space is of pivotal importance to study the potential link between species in space and life on Earth. COMs like the isomers of C2H4O2, i.e., glycolaldehyde (HCOCH2OH), acetic acid (CH3COOH), and methyl formate (HCOOCH3), have been observed abundantly around the Galactic centre, in dark clouds, and hot cores of the interstellar medium (ISM), as well as in some comets of the Solar System (e.g., Favre et al. 2011; Bockelee-Morvan et al. 2000). However, their exact gas-grain formation and destruction pathway is still unclear (Balucani et al. 2015). According to El-Abd et al. (2019), the observed column densities of methyl formate and acetic acid are well-correlated, and are likely simply tracking the relative total gas mass in star forming regions. Methyl formate and glycolaldehyde, however, display a stark dichotomy in their relative column densities. The latter finding implies that different formation/destruction routes are at play for the three isomers. To date, there is a strong laboratory evidence for an efficient production of glycolaldehyde, methyl formate, and acetic acid in the ISM through energetic processing of methanol-rich interstellar ices (Gerakines et al. 1996; Bennett and Kaiser 2007; Oberg et al. 2009; Modica and Palumbo 2010; de Barros et al. 2011; Modica et al. 2012). However, so far models and laboratory studies cannot fully reproduce the observed mutually exclusive presence of specific isomers in certain star formation regions. Understanding the formation of the C2H4O2 isomers is an important step to verify the formation of yet more complex molecules that are necessary for life. In this talk, I will present our latest results obtained at the ion accelerator ATOMKI facility in Debrecen (Hungary) using the novel ultrahigh vacuum ICA end station. Following a systematic approach, we have exposed mixtures of CO:CH3OH (1:1, 1:2, 2:1) to 200 keV and 1 MeV H+ at 20 K. Ices are monitored by means of FTIR spectroscopy and results compared with those from the analogue irradiation of a series of pure species including CO, CO2, CH4, CH3OH, methyl formate, and acetic acid. Results will be discussed in light of upcoming JWST mission. REFERENCES Favre et al. HCOOCH3 as a probe of temperature and structure in Orion-KL. A&A 532, A32, 2011 Bockelee-Morvan et al. New molecules found in comet C/1995 O1 (Hale-Bopp). Investigating the link between cometary and interstellar material. A&A, v.353, p.1101-1114, 2000 Balucani et al. Formation of complex organic molecules in cold objects: the role of gas-phase reactions, Monthly Notices of the Royal Astronomical Society: Letters, Volume 449, Issue 1, 01, Pages L16–L20, 2015 El-Abd et al. Interstellar Glycolaldehyde, Methyl Formate, and Acetic Acid. I. A Bimodal Abundance Pattern in Star-forming Regions. ApJ, 883:129 (24pp), 2019 Gerakines et al. Ultraviolet processing of interstellar ice analogs: I. Pure ices. Astronomy and Astrophysics 312(1):289-305, 1996 Bennett and Kaiser. On the Formation of Glycolaldehyde (HCOCH2OH) and Methyl Formate (HCOOCH3) in Interstellar Ice Analogs. ApJ 661 899, 2007 Oberg et al. Formation rates of complex organics in UV irradiated CH_3OH-rich ices. I. Experiments. A&A, Volume 504, Issue 3, pp.891-913, 2009 Modica and Palumbo. Formation of methyl formate after cosmic ion irradiation of icy grain mantle. A&A 519, A22, 2010 de Barros et al. Cosmic ray impact on astrophysical ices: laboratory studies on heavy ion irradiation of methane. A&A 531, A160, 2011 Modica et al. Formation of methyl formate in comets by irradiation of methanol-bearing ices. Planetary and Space Science. 73(1):425–429, 2012

The modelling of molecular excitation and dissociation processes relevant to astrochemistry requires the validation of theories by comparison with data generated from laboratory experimentation. The newly commissioned Ice Chamber for Astrophysics-Astrochemistry (ICA) allows for the study of astrophysical ice analogues and their evolution when subjected to energetic processing, thus simulating the processes and alterations interstellar icy grain mantles and icy outer Solar System bodies undergo. ICA is an ultra-high vacuum compatible chamber containing a series of IR-transparent substrates upon which the ice analogues may be deposited at temperatures of down to 20 K. Processing of the ices may be performed in one of three ways: (i) ion impacts with projectiles delivered by a 2 MV Tandetron-type accelerator, (ii) electron irradiation from a gun fitted directly to the chamber, and (iii) thermal processing across a temperature range of 20-300 K. The physico-chemical evolution of the ices is studied in situ using FTIR absorbance spectroscopy and quadrupole mass spectrometry. In this paper, we present an overview of the ICA facility with a focus on characterising the electron beams used for electron impact studies, as well as reporting the preliminary results obtained during electron irradiation and thermal processing of selected ices., Comment: Published in European Physical Journal Part D: Atomic, Molecular, Optical, and Plasma Physics

Sulfur is the tenth most abundant element in the universe and is known to play a significant role in biological systems. Accordingly, in recent years there has been increased interest in the role of sulfur in astrochemical reactions and planetary geology and geochemistry. Among the many avenues of research currently being explored is the laboratory processing of astrophysical ice analogues. Such research involves the synthesis of an ice of specific morphology and chemical composition at temperatures and pressures relevant to a selected astrophysical setting (such as the interstellar medium or the surfaces of icy moons). Subsequent processing of the ice under conditions that simulate the selected astrophysical setting commonly involves radiolysis, photolysis, thermal processing, neutral-neutral fragment chemistry, or any combination of these, and has been the subject of several studies. The in-situ changes in ice morphology and chemistry occurring during such processing has been monitored via spectroscopic or spectrometric techniques. In this paper, we have reviewed the results of laboratory investigations concerned with sulfur chemistry in several astrophysical ice analogues. Specifically, we review (i) the spectroscopy of sulfur-containing astrochemical molecules in the condensed phase, (ii) atom and radical addition reactions, (iii) the thermal processing of sulfur-bearing ices, (iv) photochemical experiments, (v) the non-reactive charged particle radiolysis of sulfur-bearing ices, and (vi) sulfur ion bombardment of and implantation in ice analogues. Potential future studies in the field of solid phase sulfur astrochemistry are also discussed in the context of forthcoming space missions, such as the NASA James Webb Space Telescope and the ESA Jupiter Icy Moons Explorer mission., Peer-reviewed version accepted for publication in Space Science Reviews

Amorphous solid water (ASW) is abundantly present in the interstellar medium, where it forms a mantle on interstellar dust particles and it is the precursor for cometary ices. In space, ASW acts as substrate for interstellar surface chemistry leading to complex molecules and it is postulated to play a critical role in proton-transfer reactions. Although ASW is widely studied and is generally well characterized by different techniques, energetically-induced structural changes, such as ion, electron and photon irradiation, in these materials are less well understood. Selective pumping of specific infrared (IR) vibrational modes can aid in understanding the role of vibrations in restructuring of hydrogen bonding networks. Here we present the first experimental results on hydrogen bonding changes in ASW induced by the intense, nearly monochromatic mid-IR free-electron laser (FEL) radiation of the FELIX-2 beamline at the FELIX Laboratory at the Radboud University in Nijmegen, the Netherlands. The changes are monitored by reflection-absorption infrared spectroscopy. Upon resonant irradiation, a modification in IR absorption band profile of ASW is observed in agreement with a growing crystalline-like contribution and a decreasing amorphous contribution. This phenomenon saturates within a few minutes of FEL irradiation, modifying upwards of 94~\% of the irradiated ice. The effect is further analysed in terms of hydrogen bonding donors and acceptors and the experiments are complimented with Molecular Dynamics simulations to constrain the effect at the molecular level., Comment: Accepted for publication in J. Phys. Chem. C

The adjustment of experimental parameters in interstellar ice analogues can have profound effects on molecular synthesis within an ice system. We demonstrated this by systematically investigating the stoichiometric mixing ratios of CO

Spectroscopic studies play a key role in the identification and analysis of interstellar ices and their structure. Some molecules have been identified within the interstellar ices either as pure, mixed, or even as layered structures. Absorption band features of water ice can significantly change with the presence of different types of impurities (CO, CO2, CH3OH, H2CO, etc.). In this work, we carried out a theoretical investigation to understand the behavior of water band frequency, and strength in the presence of impurities. The computational study has been supported and complemented by some infrared spectroscopy experiments aimed at verifying the effect of HCOOH, NH3 , and CH3 OH on the band profiles of pure H2O ice. Specifically, we explored the effect on the band strength of libration, bending, bulk stretching, and free-OH stretching modes. Computed band strength profiles have been compared with our new and existing experimental results, thus pointing out that vibrational modes of H2O and their intensities can change considerably in the presence of impurities at different concentrations. In most cases, the bulk stretching mode is the most affected vibration, while the bending is the least affected mode. HCOOH was found to have a strong influence on the libration, bending, and bulk stretching band profiles. In the case of NH3, the free-OH stretching band disappears when the impurity concentration becomes 50%. This work will ultimately aid a correct interpretation of future detailed spaceborne observations of interstellar ices by means of the upcoming JWST mission., Comment: Accepted for Publication in the ACS Earth and Space Chemistry Journal

Methane is one of the simplest stable molecules that is both abundant and widely distributed across space. It is thought to have partial origin from interstellar molecular clouds, which are near the beginning of the star formation cycle. Observational surveys of CH$_4$ ice towards low- and high-mass young stellar objects showed that much of the CH$_4$ is expected to be formed by the hydrogenation of C on dust grains, and that CH$_4$ ice is strongly correlated with solid H$_2$O. Yet, this has not been investigated under controlled laboratory conditions, as carbon-atom chemistry of interstellar ice analogues has not been experimentally realized. In this study, we successfully demonstrate with a C-atom beam implemented in an ultrahigh vacuum apparatus the formation of CH$_4$ ice in two separate co-deposition experiments: C + H on a 10 K surface to mimic CH$_4$ formation right before H$_2$O ice is formed on the dust grain, and C + H + H$_2$O on a 10 K surface to mimic CH$_4$ formed simultaneously with H$_2$O ice. We confirm that CH$_4$ can be formed by the reaction of atomic C and H, and that the CH$_4$ formation rate is 2 times greater when CH$_4$ is formed within a H$_2$O-rich ice. This is in agreement with the observational finding that interstellar CH$_4$ and H$_2$O form together in the polar ice phase, i.e., when C- and H-atoms simultaneously accrete with O-atoms on dust grains. For the first time, the conditions that lead to interstellar CH$_4$ (and CD$_4$) ice formation are reported, and can be incorporated into astrochemical models to further constrain CH$_4$ chemistry in the interstellar medium and in other regions where CH$_4$ is inherited.

The adjustment of experimental parameters in interstellar ice analogues can have profound effects on molecular synthesis within an ice system. We demonstrated this by systematically investigating the stoichiometric mixing ratios of CO2 : NH3 ices as a function of thermal processing using mid-IR and VUV spectroscopy. We observed that the type of CO2 bonding environment was dependent on the different stoichiometric mixing ratios and that this pre-determined the NH3 crystallite structure after phase change. The thermal reactivity of the ices was linked to the different chemical and physical properties of the stoichiometric ratios. Our results provide new details into the chemical and physical properties of the different stoichiometric CO2 : NH3 ices enhancing our understanding of the thermally induced molecular synthesis within this ice system.

Understanding how complex organic molecules (COMs) form, survive under space conditions and are then delivered to planetesimals in Solar-like systems is a key step to unravelling the origin of the life on Earth [1]. From dedicated laboratory studies it has become clear that the large molecular inventory observed in space cannot be formed efficiently in the gas phase. Interstellar dust grains provide surfaces on which gas-phase species can accrete, collide and react, and to which they can donate excess energy. Therefore, in dense interstellar clouds, icy dust grains act both as a molecular reservoir and as sites for catalysis [2]. For decades, surface complex molecule formation has been thought to be triggered largely by energetic processing, e.g. photon, electron and cosmic ray bombardment of ice dust grains [3]. Similarly, the rich inventory of molecules found by the Rosetta mission in the surface ices of comet 67P/Churyumov–Gerasimenko [4] and the increasing studies of composition of ices on planetary bodies (e.g. Saturnian and Jovian moons, Pluto, Charon and Kuiper belt objects) all suggest molecular synthesis by irradiation by ion bombardment. However, comprehensive laboratory studies of such ice analogues systematically exposed to a wide range of ions and energies remain fragmentary and often contradictory. Further laboratory work is therefore pivotal to our understanding of the chemical and physical processes in the ISM and on planetary bodies of the Solar System to interpret data from past, present and future space missions (e.g. JWST, JUICE). At Atomki in Debrecen, Hungary, we have recently commissioned a new ion beamline dedicated to exploring the processing of complex molecular ices found in the interstellar medium and Solar System. It is a Transnational Access facility for the EUROPLANET 2024 Research Infrastructure Project and is therefore open to the international research community (https://www.europlanet-society.org/europlanet-2024-ri/ta2-dplf/ta2-facility-11-atomki-ice-chamber-for-astrophysics-astrochemistry-ica/ ). High current beams can be provided from H to a wide range of heavy ions with the kinetic energy of 0.2 – 20 MeV. The Ice Chamber for Astrophysics/Astrochemistry (ICA) at Atomki is designed to investigate the effect of ion irradiation of astrophysically relevant ices deposited on a series of cold substrates (20-300 K) vertically mounted on a copper holder connected to a closed cycle cryostat, a 360° rotation stage and a z-linear manipulator. The ice layers are created through background deposition of gases, both pure and mixed, which are prepared in a high vacuum dosing-line and introduced in the main chamber by means of an all leak metal valve not facing the sample holder. The ice structure can be crystalline or amorphous depending on the chosen temperature during deposition. The apparatus is currently being upgraded in order to study cold layers of more complex organic molecules produced by an effusive evaporator. The ice composition grown on an infrared transparent substrate and the physico-chemical changes induced upon ion irradiation are monitored by a FTIR spectrometer in transmission mode. Using metallic substrates, reflection mode is also possible. Ions of different species and charge states mimicking the effects of cosmic rays and stellar wind are produced by a Tandetron accelerator. The ICA chamber is also equipped with an electron gun, which provides electron beams of a few microamps in the 5 eV – 2 keV energy range. Sequential and/or simultaneous irradiation by ions and electrons is an available option for studying radiation synergies. Temperature programed desorption (TPD) studies can be performed on both non-irradiated and irradiated ices. The desorbed molecules during irradiation and TPD experiments are monitored by a quadrupole mass spectrometer, while chemical and morphological changes in the ice can be followed “in situ” by using the FTIR spectrometer. At the conference, we will present the preliminary results of the e-, H+ and S2+ impact on pure methanol ice and some other ice mixtures deposited at 20 K as a function of a wide range of energies and beam fluxes. We will further discuss how the induced chemical changes strongly dependent on the studied parameters. Acknowledgment Europlanet 2024 RI has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 871149. The enthusiastic help from the Atomki Tandetron accelerator staff both in preparation and experiments is gratefully acknowledged. References [1] E. Herbst, and E. F. van Dishoeck, Complex organic interstellar molecules,Annu. Rev. Astron. Astrophys. 47 (2009), 427-480 [2] A. C. A. Boogert, P. A. Gerakines, and D. C. Whittet, Observations of theicy universe, Annu. Rev. Astron. Astrophys. 53 (2015), 541-581 [3] M. A. Allodi, R. A. Baragiola, G. A. Baratta, M. A. Barucci, G. A. Blake,Ph. Boduch, J. R. Brucato, C. Contreras, S. H. Cuylle, D. Fulvio, M. S.Gudipati, S. Ioppolo, Z. Kanuchová, A. Lignell, H. Linnartz, M. E. Palumbo, U. Raut, H. Rothard, F. Salama, E. V. Savchenko, E. Sciamma-OBrien, G.Strazzulla, Complementary and emerging techniques for astrophysical icesprocessed in the laboratory, Space Sci. Rev., 180 (2013) 101 [4] Altwegg, Kathrin; et al. (27 May 2016). Prebiotic chemicals—amino acid and phosphorus—in the coma of comet 67P/Churyumov-Gerasimenko. Science Advances. 2 (5): e1600285. Bibcode:2016SciA....2E0285A. doi:10.1126/sciadv.1600285. PMC 4928965. PMID 27386550.

Simple and complex organic molecules (COMs) are observed along different phases of star and planet formation and have been successfully identified in prestellar environments such as dark and translucent clouds. Yet the picture of organic molecule formation at those earliest stages of star formation is not complete and an important reason is the lack of specific laboratory experiments that simulate carbon atom addition reactions on icy surfaces of interstellar grains. Here we present experiments in which CO molecules as well as C- and H-atoms are co-deposited with H$_2$O molecules on a 10 K surface mimicking the ongoing formation of an "H$_2$O-rich" ice mantle. To simulate the effect of impacting C-atoms and resulting surface reactions with ice components, a specialized C-atom beam source is used, implemented on SURFRESIDE$^3$, an UHV cryogenic setup. Formation of ketene (CH$_2$CO) in the solid state is observed "in situ" by means of reflection absorption IR spectroscopy. C$^1$$^8$O and D isotope labelled experiments are performed to further validate the formation of ketene. Data analysis supports that CH$_2$CO is formed through C-atom addition to a CO-molecule, followed by successive hydrogenation transferring the formed :CCO into ketene. Efficient formation of ketene is in line with the absence of an activation barrier in C+CO reaction reported in the literature. We also discuss and provide experimental evidence for the formation of acetaldehyde (CH$_3$CHO) and possible formation of ethanol (CH$_3$CH$_2$OH), two COM derivatives of CH$_2$CO hydrogenation. The underlying reaction network is presented and the astrochemical implications of the derived pathways are discussed., Accepted by ApJ

A long standing problem in astrochemistry is the inability of many current models to account for missing sulfur content. Many relatively simple species that may be good candidates to sequester sulfur have not been measured experimentally at the high spectral resolution necessary to enable radioastronomical identification. On the basis of new laboratory data, we report searches for the rotational lines in the microwave, millimeter, and sub-millimeter regions of the sulfur-containing hydrocarbon HCCSH. This simple species would appear to be a promising candidate for detection in space owing to the large dipole moment along its $b$-inertial axis, and because the bimolecular reaction between two highly abundant astronomical fragments (CCH and SH radicals) may be rapid. An inspection of multiple line surveys from the centimeter to the far-infrared toward a range of sources from dark clouds to high-mass star-forming regions, however, resulted in non-detections. An analogous search for the lowest-energy isomer, H$_2$CCS, is presented for comparison, and also resulted in non-detections. Typical upper limits on the abundance of both species relative to hydrogen are $10^{-9}$-$10^{-10}$. We thus conclude that neither isomer is a major reservoir of interstellar sulfur in the range of environments studied. Both species may still be viable candidates for detection in other environments or at higher frequencies, providing laboratory frequencies are available., Accepted in the Astrophysical Journal

A number of recent experimental studies have shown that solid-state complex organic molecules (COMs) can form under conditions that are relevant to the CO freeze-out stage in dense clouds. In this work, we show that alcohols can be formed well before the CO freeze-out stage (i.e., in the H2O-rich ice phase). This joint experimental and computational investigation shows that the isomers, n- and i-propanol (H3CCH2CH2OH and H3CCHOHCH3) and n- and i-propenol (H3CCHCHOH and H3CCOHCH2), can be formed in radical-addition reactions starting from propyne (H3CCCH) + OH at the low temperature of 10 K, where H3CCCH is one of the simplest representatives of stable carbon chains already identified in the interstellar medium (ISM). The resulting average abundance ratio of 1:1 for n-propanol:i-propanol is aligned with the conclusions from the computational work that the geometric orientation of strongly interacting species is influential to the extent of which 'mechanism' is participating, and that an assortment of geometries leads to an averaged-out effect. Three isomers of propanediol are also tentatively identified in the experiments. It is also shown that propene and propane (H3CCHCH2 and H3CCH2CH3) are formed from the hydrogenation of H3CCCH. Computationally-derived activation barriers give additional insight into what types of reactions and mechanisms are more likely to occur in the laboratory and in the ISM. Our findings not only suggest that the alcohols studied here share common chemical pathways and therefore can show up simultaneously in astronomical surveys, but also that their extended counterparts that derive from polyynes containing H3C(CC)nH structures may exist in the ISM. Such larger species, like fatty alcohols, are the possible constituents of simple lipids that primitive cell membranes on the early Earth are thought to be partially composed of., Published in ACS Earth and Space Chemistry, Complex Organic Molecules (COMs) in Star-Forming Regions special issue

1-propanol (CH3CH2CH2OH) is a three carbon-bearing representative of primary linear alcohols that may have its origin in the cold dark cores in interstellar space. To test this, we investigated in the laboratory whether 1-propanol ice can be formed along pathways possibly relevant to the prestellar core phase. We aim to show in a two-step approach that 1-propanol can be formed through reaction steps that are expected to take place during the heavy CO freeze-out stage by adding C2H2 into the CO + H hydrogenation network via the formation of propanal (CH3CH2CHO) as an intermediate and its subsequent hydrogenation. Temperature programmed desorption-quadrupole mass spectrometry (TPD-QMS) is used to identify the newly formed propanal and 1-propanol. Reflection absorption infrared spectroscopy (RAIRS) is used as a complementary diagnostic tool. The mechanisms that can contribute to the formation of solid-state propanal and 1-propanol, as well as other organic compounds, during the heavy CO freeze-out stage are constrained by both laboratory experiments and theoretical calculations. Here it is shown that recombination of HCO radicals, formed upon CO hydrogenation, with radicals formed upon C2H2 processing - H2CCH and H3CCH2 - offers possible reaction pathways to solid-state propanal and 1-propanol formation. This extends the already important role of the CO hydrogenation chain in the formation of larger COMs (complex organic molecules). The results are used to compare with ALMA observations. The resulting 1-propanol:propanal ratio concludes an upper limit of < 0:35-0:55, which is complemented by computationally-derived activation barriers in addition to the experimental results., Accepted for publication in Astronomy and Astrophysics

Formic acid (HCOOH) and carbon dioxide (CO2) are simple species that have been detected in the interstellar medium. The solid-state formation pathways of these species under experimental conditions relevant to prestellar cores are primarily based off of weak infrared transitions of the HOCO complex and usually pertain to the H2O-rich ice phase, and therefore more experimental data are desired. In this article, we present a new and additional solid-state reaction pathway that can form HCOOH and CO2 ice at 10 K 'non-energetically' in the laboratory under conditions related to the "heavy" CO freeze-out stage in dense interstellar clouds, i.e., by the hydrogenation of an H2CO:O2 ice mixture. This pathway is used to piece together the HCOOH and CO2 formation routes when H2CO or CO reacts with H and OH radicals. Temperature programmed desorption - quadrupole mass spectrometry (TPD-QMS) is used to confirm the formation and pathways of newly synthesized ice species as well as to provide information on relative molecular abundances. Reflection absorption infrared spectroscopy (RAIRS) is additionally employed to characterize reaction products and determine relative molecular abundances. We find that for the conditions investigated in conjunction with theoretical results from the literature, H+HOCO and HCO+OH lead to the formation of HCOOH ice in our experiments. Which reaction is more dominant can be determined if the H+HOCO branching ratio is more constrained by computational simulations, as the HCOOH:CO2 abundance ratio is experimentally measured to be around 1.8:1. H+HOCO is more likely than OH+CO (without HOCO formation) to form CO2. Isotope experiments presented here further validate that H+HOCO is the dominant route for HCOOH ice formation in a CO-rich CO:O2 ice mixture that is hydrogenated. These data will help in the search and positive identification of HCOOH ice in prestellar cores., Comment: Accepted for publication in Astronomy and Astrophysics

We present new experimental results on the formation of polyynes by 1 keV electron irradiation of simple hydrocarbons and their mixtures with N2 and H2O under conditions that mimic the physical conditions on the grains in the dense molecular clouds in the interstellar medium (ISM) and the surfaces of small bodies and icy satellites in our Solar System.

Interstellar ice dust grains are the place where prebiotic molecules that feeds nascent solar-like systems, including planets and planetesimals, form. Recent ALMA observation of complex organic molecules (COMs) in cold dark clouds and the upcoming JWST mission highlight the importance of the interplay between gas and dust to the formation and survival of COMs in space throughout the process of star and planet formation. In this talk, I will present recent laboratory work on the formation and destruction of COMs in the solid phase under dark molecular cloud conditions. During the talk, I will show and compare energetic (UV photolysis) and non-energetic (atom bombardment) routes. This laboratory work ultimately contributes to our understanding of the origin of life in the Universe.

Icy grain mantles are the main reservoir for volatile elements in star-forming regions across the Universe, as well as the formation site of pre-biotic complex organic molecules (COMs) seen in our Solar System. Through the IceAge Early Release Science program, we will trace the evolution of pristine and complex ice chemistry in a representative low-mass star-forming region through observations of a: pre-stellar core, Class 0 protostar, Class I protostar, and protoplanetary disk. Comparing high spectral resolution (R~1500-3000) and sensitivity (S/N~100-300) observations from 3 to 15 micron to template spectra, we will map the spatial distribution of ices down to ~20-50 AU in these targets to identify when, and at what visual extinction, the formation of each ice species begins. Such high-resolution spectra will allow us to search for new COMs, as well as distinguish between different ice morphologies, thermal histories, and mixing environments.The analysis of these data will result in science products beneficial to Cycle 2 proposers. A newly updated public laboratory ice database will provide feature identifications for all of the expected ices, while a chemical model fit to the observed ice abundances will be released publically as a grid, with varied metallicity and UV fields to simulate other environments. We will create improved algorithms to extract NIRCAM WFSS spectra in crowded fields with extended sources as well as optimize the defringing of MIRI LRS spectra in order to recover broad spectral features. We anticipate that these resources will be particularly useful for astrochemistry and spectroscopy of fainter, extended targets like star forming regions of the SMC/LMC or more distant galaxies.

The formation of methanol (CH3OH) on icy grain mantles during the star formation cycle is mainly associated with the CO freeze-out stage. Yet there are reasons to believe that CH3OH also can form at an earlier period of interstellar ice evolution in CO-poor and H2O-rich ices. This work focuses on CH3OH formation in a H2O-rich interstellar ice environment following the OH-mediated H-abstraction in the reaction, CH4 + OH. Experimental conditions are systematically varied to constrain the CH3OH formation yield at astronomically relevant temperatures. CH4, O2, and hydrogen atoms are co-deposited in an ultrahigh vacuum chamber at 10-20 K. OH radicals are generated by the H + O2 surface reaction. Temperature programmed desorption - quadrupole mass spectrometry (TPD-QMS) is used to characterize CH3OH formation, and is complemented with reflection absorption infrared spectroscopy (RAIRS) for CH3OH characterization and quantitation. CH3OH formation is shown to be possible by the sequential surface reaction chain, CH4 + OH -> CH3 + H2O and CH3 + OH -> CH3OH at 10-20 K. This reaction is enhanced by tunneling, as noted in a recent theoretical investigation (Lamberts et al. 2017). The CH3OH formation yield via the CH4 + OH route versus the CO + H route is approximately 20 times smaller for the laboratory settings studied. The astronomical relevance of the new formation channel investigated here is discussed., Accepted for publication in Astronomy and Astrophysics

Context. In dense clouds, hydrogenation reactions on icy dust grains are key in the formation of molecules, like formaldehyde, methanol, and complex organic molecules (COMs). These species form through the sequential hydrogenation of CO ice. Although molecular hydrogen (H2) abundances can be four orders of magnitude higher than those of free H-atoms in dense clouds, H2 surface chemistry has been largely ignored; several laboratory studies show that H2 does not actively participate in non-energetic ice chemistry because of the high activation energies required. Aims. For the example of CO ice hydrogenation, we experimentally investigated the potential role of H2 molecules on the surface chemistry when energetic processing (i.e., UV photolysis) is involved. We test whether additional hydrogenation pathways become available upon UV irradiation of a CO:H2 ice mixture and whether this reaction mechanism also applies to other chemical systems. Methods. Ultra-high vacuum (UHV) experiments were performed at 8~20 K. A pre-deposited solid mixture of CO:H2 was irradiated with UV-photons. Reflection absorption infrared spectroscopy (RAIRS) was used as an in situ diagnostic tool. Single reaction steps and possible isotopic effects were studied by comparing results from CO:H2 and CO:D2 ice mixtures. Results. After UV-irradiation of a CO:H2 ice mixture, two photon-induced products, HCO and H2CO, are unambiguously detected. The proposed reaction mechanism involves electronically excited CO in the following reaction steps: CO + h��->CO*, CO* + H2->HCO + H where newly formed H-atoms are then available for further hydrogenation reactions. The HCO formation yields have a strong temperature dependence for the investigated regime, which is most likely linked to the H2 sticking coefficient. Finally, the astronomical relevance of this photo-induced reaction channel is discussed., 8 pages, 6 figures

The pore structure of vapour deposited ASW is poorly understood, despite its importance to fundamental processes such as grain chemistry, cooling of star forming regions, and planet formation. We studied structural changes of vapour deposited D2O on intra-molecular to 30 nm length scales at temperatures ranging from 18 to 180 K and observed enhanced mobility from 100 to 150 K. An Arrhenius type model describes the loss of surface area and porosity with a common set of kinetic parameters. The low activation energy (428 K) is commensurate with van der Waals forces between nm-scale substructures in the ice. Our findings imply that water porosity will always change with time, even at low temperatures.

This study focuses on the formation of two molecules of astrobiological importance - glycolaldehyde (HC(O)CH2OH) and ethylene glycol (H2C(OH)CH2OH) - by surface hydrogenation of CO molecules. Our experiments aim at simulating the CO freeze-out stage in interstellar dark cloud regions, well before thermal and energetic processing become dominant. It is shown that along with the formation of H2CO and CH3OH - two well established products of CO hydrogenation - also molecules with more than one carbon atom form. The key step in this process is believed to be the recombination of two HCO radicals followed by the formation of a C-C bond. The experimentally established reaction pathways are implemented into a continuous-time random-walk Monte Carlo model, previously used to model the formation of CH3OH on astrochemical time-scales, to study their impact on the solid-state abundances in dense interstellar clouds of glycolaldehyde and ethylene glycol.

The surface formation of NH3 and its deuterated isotopologues – NH_2D, NHD_2, and ND_3 – is investigated at low temperatures through the simultaneous addition of hydrogen and deuterium atoms to nitrogen atoms in CO-rich interstellar ice analogues. The formation of all four ammonia isotopologues is only observed up to 15 K, and drops below the detection limit for higher temperatures. Differences between hydrogenation and deuteration yields result in a clear deviation from a statistical distribution in favour of deuterium enriched species. The data analysis suggests that this is due to a higher sticking probability of D atoms to the cold surface, a property that may generally apply to molecules that are formed in low temperature surface reactions. The results found here are used to interpret ammonia–deuterium fractionation as observed in pre-protostellar cores.

Complex organic molecules (COMs) have been identified in different environments in star- forming regions. Laboratory studies show that COMs form in the solid state, on icy grains, typically following a non-energetic (atom-addition) or energetic (UV-photon absorption) trigger. So far, such studies have been largely performed for single processes. Here, we present the first work that quantitatively investigates both the relative importance and the cumulative effect of (non-)energetic processing. We focus on astronomically relevant CO:CH3OH = 4:1 ice analogues exposed to doses relevant for the collapse stage of dense clouds. Hydrogenation experiments result in the formation of methyl formate (MF HC(O)OCH3), glycolaldehyde (GA HC(O)CH2OH) and ethylene glycol (EG H2C(OH)CH2OH) at 14 K. The absolute abundances and the abundance fractions are found to be dependent on the H-atom/CO-CH3OH molecule ratios and on the overall deposition rate. In the case that ices are exposed to UV photons only, several different COMs are found. Typically, the abundance fractions are 0.2 for MF, 0.3 for GA and 0.5 for EG as opposed to the values found in pure hydrogenation experiments without UV in which MF is largely absent: 0.0, 0.2-0.6 and 0.8-0.4, respectively. In experiments where both are applied, overall COM abundances drop to about half of those found in the pure UV irradiation experiments, but the composition fractions are very similar. This implies COM ratios can be used as a diagnostic tool to derive the processing history of an ice. Solid-state branching ratios derived here for GA and EG compare well with observations, while the MF case cannot be explained by solid-state conditions investigated here., Comment: 14 pages, 8 figures, 1 table

Observational studies reveal that complex organic molecules (COMs) can be found in various objects associated with different star formation stages. The identification of COMs in prestellar cores, i.e., cold environments in which thermally induced chemistry can be excluded and radiolysis is limited by cosmic rays and cosmic ray induced UV-photons, is particularly important as this stage sets up the initial chemical composition from which ultimately stars and planets evolve. Recent laboratory results demonstrate that molecules as complex as glycolaldehyde and ethylene glycol are efficiently formed on icy dust grains via non-energetic atom addition reactions between accreting H atoms and CO molecules, a process that dominates surface chemistry during the 'CO-freeze out stage' in dense cores. In the present study we demonstrate that a similar mechanism results in the formation of the biologically relevant molecule glycerol - HOCH2CH(OH)CH2OH - a three-carbon bearing sugar alcohol necessary for the formation of membranes of modern living cells and organelles. Our experimental results are fully consistent with a suggested reaction scheme in which glycerol is formed along a chain of radical-radical and radical-molecule interactions between various reactive intermediates produced upon hydrogenation of CO ice or its hydrogenation products. The tentative identification of the chemically related simple sugar glyceraldehyde - HOCH2CH(OH)CHO - is discussed as well. These new laboratory findings indicate that the proposed reaction mechanism holds much potential to form even more complex sugar alcohols and simple sugars., Accepted for publication in The Astrophysical Journal

The cross-disciplinary field of astrochemistry exists to understand the formation, destruction, and survival of molecules in astrophysical environments. Molecules in space are synthesized via a large variety of gas-phase reactions, and reactions on dust-grain surfaces, where the surface acts as a catalyst. A broad consensus has been reached in the astrochemistry community on how to suitably treat gas-phase processes in models, and also on how to present the necessary reaction data in databases; however, no such consensus has yet been reached for grain-surface processes. A team of ${\sim}25$ experts covering observational, laboratory and theoretical (astro)chemistry met in summer of 2014 at the Lorentz Center in Leiden with the aim to provide solutions for this problem and to review the current state-of-the-art of grain surface models, both in terms of technical implementation into models as well as the most up-to-date information available from experiments and chemical computations. This review builds on the results of this workshop and gives an outlook for future directions.

Solid state astrochemical reaction pathways have the potential to link the formation of small nitrogen-bearing species, like NH3 and HNCO, and prebiotic molecules, specifically amino acids. To date, the chemical origin of such small nitrogen containing species is still not well understood, despite the fact that ammonia is an abundant constituent of interstellar ices toward young stellar objects and quiescent molecular clouds. This is mainly because of the lack of dedicated laboratory studies. The aim of the present work is to experimentally investigate the formation routes of NH3 and HNCO through non-energetic surface reactions in interstellar ice analogues under fully controlled laboratory conditions and at astrochemically relevant temperatures. This study focuses on the formation of NH3 and HNCO in CO-rich (non-polar) interstellar ices that simulate the CO freeze-out stage in dark interstellar cloud regions, well before thermal and energetic processing start to become relevant. We demonstrate and discuss the surface formation of solid HNCO through the interaction of CO molecules with NH radicals - one of the intermediates in the formation of solid NH3 upon sequential hydrogenation of N atoms. The importance of HNCO for astrobiology is discussed.

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.

Water is the most abundant molecule found in interstellar icy mantles. In space it is thought to be efficiently formed on the surfaces of dust grains through successive hydrogenation of O, O2 and O3. The underlying physico-chemical mechanisms have been studied experimentally in the past decade and in this paper we extend this work theoretically, using Continuous-Time Random-Walk Monte Carlo simulations to disentangle the different processes at play during hydrogenation of molecular oxygen. CTRW-MC offers a kinetic approach to compare simulated surface abundances of different species to the experimental values. For this purpose, the results of four key experiments-sequential hydrogenation as well as co-deposition experiments at 15 and 25 K-are selected that serve as a reference throughout the modeling stage. The aim is to reproduce all four experiments with a single set of parameters. Input for the simulations consists of binding energies as well as reaction barriers (activation energies). In order to understand the influence of the parameters separately, we vary a single process rate at a time. Our main findings are: (i) The key reactions for the hydrogenation route starting from O2 are H + O2, H + HO2, OH + OH, H + H2O2, H + OH. (ii) The relatively high experimental abundance of H2O2 is due to its slow destruction. (iii) The large consumption of O2 at a temperature of 25 K is due to a high hydrogen diffusion rate. (iv) The diffusion of radicals plays an important role in the full reaction network. The resulting set of 'best fit' parameters is presented and discussed for use in future astrochemical modeling.