Cospatial ice mapping of H2O with CO2 and CO across a molecular cloud with JWST/NIRCam

The diffusion of species in icy dust grain mantles is a fundamental process that shapes the chemistry of interstellar regions; yet, measurements of diffusion in interstellar ice analogs are scarce. Here we present measurements of CO diffusion into CO2 ice at low temperatures (T = 11–23 K) using CO2 longitudinal optical phonon modes to monitor the level of mixing of initially layered ices. We model the diffusion kinetics using Fick’s second law and find that the temperature-dependent diffusion coefficients are well fit by an Arrhenius equation, giving a diffusion barrier of 300 ± 40 K. The low barrier along with the diffusion kinetics through isotopically labeled layers suggest that CO diffuses through CO2 along pore surfaces rather than through bulk diffusion. In complementary experiments, we measure the desorption energy of CO from CO2 ices deposited at 11–50 K by temperature programmed desorption and find that the desorption barrier ranges from 1240 ± 90 K to 1410 ± 70 K depending on the CO2 deposition temperature and resultant ice porosity. The measured CO–CO2 desorption barriers demonstrate that CO binds equally well to CO2 and H2O ices when both are compact. The CO–CO2 diffusion–desorption barrier ratio ranges from 0.21 to 0.24 dependent on the binding environment during diffusion. The diffusion–desorption ratio is consistent with the above hypothesis that the observed diffusion is a surface process and adds to previous experimental evidence on diffusion in water ice that suggests surface diffusion is important to the mobility of molecules within interstellar ices.

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, H2surface chemistry has been largely ignored; several laboratory studies show that H2does 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 H2molecules 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:H2ice 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:H2was 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:H2and CO:D2ice mixtures.Results.After UV-irradiation of a CO:H2ice 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 + hν→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 H2sticking coefficient. Moreover, the derived formation cross section reflects a cumulative reaction rate that mainly determined by both the H-atom diffusion rate and initial concentration of H2at 8–20 K and that is largely determined by the H2sticking coefficient. Finally, the astronomical relevance of this photo-induced reaction channel is discussed.

Context. Icy dust grains play an important role in the formation of complex inter- and circumstellar molecules. Observational studies show that polycyclic aromatic hydrocarbons (PAHs) are abundantly present in the ISM in the gas phase. It is likely that these non-volatile species freeze out onto dust grains as well and participate in the astrochemical solid-state network, but experimental PAH ice studies are largely lacking. Methods. Near UV/VIS spectroscopy is used to track the in situ VUV driven photochemistry of pyrene containing ices at temperatures ranging from 10 to 125 K. Results. The main photoproducts of VUV photolyzed pyrene ices are spectroscopically identified and their band positions are listed for two host ices, \water and CO. Pyrene ionisation is found to be most efficient in \water ices at low temperatures. The reaction products, triplet pyrene and the 1-hydro-1-pyrenyl radical are most efficiently formed in higher temperature water ices and in low temperature CO ice. Formation routes and band strength information of the identified species are discussed. Additionally, the oscillator strengths of Py, Py^+ and PyH are derived and a quantitative kinetic analysis is performed by fitting a chemical reaction network to the experimental data. Conclusions. Pyrene is efficiently ionised in water ice at temperatures below 50 K. Hydrogenation reactions dominate the chemistry in low temperature CO ice with trace amounts of water. The results are put in an astrophysical context by determining the importance of PAH ionisation in a molecular cloud. The photoprocessing of a sample PAH in ice described in this manuscript indicates that PAH photoprocessing in the solid state should also be taken into account in astrochemical models.

Molecular clouds (MCs) in space are the birthplace of various molecular species. Chemical reactions occurring on the cryogenic surfaces of cosmic icy dust grains have been considered to play important roles in the formation of these species. Radical reactions are crucial because they often have low barriers and thus proceed even at low temperatures such as ∼10 K. Since the 2000s, laboratory experiments conducted under low-temperature, high-vacuum conditions that mimic MC environments have revealed the elementary physicochemical processes on icy dust grains. In this review, experiments conducted by our group in this context are explored, with a focus on radical reactions on the surface of icy dust analogues, leading to the formation of astronomically abundant molecules such as H2, H2O, H2CO, and CH3OH and deuterium fractionation processes. The development of highly sensitive, non-destructive methods for detecting adsorbates and their utilization for clarifying the behavior of free radicals on ice, which contribute to the formation of complex organic molecules, are also described.

It was in ‘The Magellanic Cloud’ (1955) – a science fiction novel by Stanislaw Lem – that engineers travelling to another star noticed that their spacecraft for unknown reasons overheated. The cause had to be outside the spaceship, but obviously there was only emptiness, at least compared to terrestrial conditions. The space between the stars, the interstellar medium (ISM), however, is not completely empty and at the high speed of the spacecraft the cross-section with impacting particles, even from such a dilute environment, was found to be sufficient to cause an overheating. Today, 60 years later, the ISM has been studied in detail by astronomical observations, reproduced in dedicated laboratory experiments and simulated by complex astrochemical models. The space between the stars is, indeed, far from empty; it comprises gas, dust and ice and the molecules detected so far are both small (diatomics) and large (long carbon chains, PAHs and fullerenes), stable and reactive (radicals, ions, and excited molecules) evidencing an exotic and fascinating chemistry, taking place at low densities, low temperatures and experiencing intense radiation fields. Astrochemists explain the observed chemical complexity in space – so far 185 different molecules (not including isotopologues) have been identified – as the cumulative outcome of reactions in the gas phase and on icy dust grains. Gas phase models explain the observed abundances of a substantial part of the observed species, but fail to explain the number densities for stable molecules, as simple as water, methanol or acetonitrile – one of the most promising precursor species for the simplest amino acid glycine – as well as larger compounds such as glycolaldehyde, dimethylether and ethylene glycol. Evidence has been found that these and other complex species, including organic ones, form on icy dust grains that act as catalytic sites for molecule formation. It is here where particles ‘accrete, meet, and greet’ (i.e. freeze out, diffuse and react) upon energetic and non-energetic processing, such as irradiation by vacuum UV light, interaction with impacting particles (atoms, electrons and cosmic rays) or heating. This review paper summarises the state-of-the-art in laboratory based interstellar ice chemistry. The focus is on atom addition reactions, illustrating how water, carbon dioxide and methanol can form in the solid state at astronomically relevant temperatures, and also the formation of more complex species such as hydroxylamine, an important prebiotic molecule, and glycolaldehyde, the smallest sugar, is discussed. These reactions are particularly relevant during the ‘dark’ ages of star and planet formation, i.e. when the role of UV light is restricted. A quantitative characterization of such processes is only possible through dedicated laboratory studies, i.e. under full control of a large set of parameters such as temperature, atom-flux, and ice morphology. The resulting numbers, physical and chemical constants, e.g. barrier heights, reaction rates and branching ratios, provide information on the molecular processes at work and are needed as input for astrochemical models, in order to bridge the timescales typical for a laboratory setting to those needed to understand the evolutionary stages of the ISM. Details of the experiments as well as the astrochemical impact of the results are 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.

Context. The study of the snow line is an important topic in several domains of astrophysics, and particularly for the evolution of proto-stellar environments and the formation of planets. Aims. The formation of the first layer of ice on carbon grains requires low temperatures compared to the temperature of evaporation (T > 100 K). This asymmetry generates a zone in which bare and icy dust grains coexist. Methods. We use Monte-Carlo simulations to describe the formation time scales of ice mantles on bare grains in protostellar disks and massive protostars environments. Then we analytically describe these two systems in terms of grain populations subject to infall and turbulence, and assume steady-state. Results. Our results show that there is an extended region beyond the snow line where icy and bare grains can coexist, in both proto-planetary disks and massive protostars. This zone is not negligible compared to the total size of the objects: on the order of 0.4 AU for proto-planetary disks and 5400 AU for high-mass protostars. Times to reach the steady-state are respectively es- timated from 10^2 to 10^5 yr. Conclusions. The presence of a zone, a so-called snow border, in which bare and icy grains co- exist can have a major impact on our knowledge of protostellar environments. From a theoretical point of view, the progression of icy grains to bare grains as the temperature increases, could be a realistic way to model hot cores and hot corinos. Also, in this zone, the formation of planetesimals will require the coagulation of bare and icy grains. Observationally, this zone allows high abundances of gas phase species at large scales, for massive protostars particularly, even at low temperatures (down to 50 K).

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 nonenergetic 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.

Ices form on the surfaces of interstellar and circumstellar dust grains though freeze-out of molecules and atoms from the gas-phase followed by chemical reactions. The composition, chemistry, structure and desorption properties of these ices regulate two important aspects of planet formation: the locations of major condensation fronts in protoplanetary disks (i.e. snow lines) and the formation efficiencies of complex organic molecules in astrophysical environments. The latter regulates the availability of prebiotic material on nascent planets. With ALMA it is possible to directly observe both (CO) snowlines and complex organics in protoplanetary disks. The interpretation of these observations requires a detailed understanding of the fundamental ice processes that regulate the build-up, evolution and desorption of icy grain mantles. This proceeding reviews how experiments on thermal CO and N2 ice desorption, UV photodesorption of CO ice, and CO diffusion in H2O ice have been used to guide and interpret astrochemical observations of snowlines and complex molecules.

Isolated dense molecular cores are investigated to study the onset of complex organic molecule formation in interstellar ice. Sampling three cores with ongoing formation of low-mass stars (B59, B335, and L483) and one starless core (L694-2), we sample lines of sight to nine background stars and five young stellar objects (YSOs; A K ∼ 0.5–4.7). Spectra of these stars from 2 to 5 μm with NASA’s Infrared Telescope Facility (IRTF) simultaneously display signatures from the cores of H2O (3.0 μm), CH3OH (C–H stretching mode, 3.53 μm), and CO (4.67 μm) ices. The CO ice is traced by nine stars, in which five show a long-wavelength wing due to a mixture of CO with polar ice (CO r ), presumably CH3OH. Two of these sightlines also show independent detections of CH3OH. For these we find the ratio of the CH3OH:CO r is 0.55 ± 0.06 and 0.73 ± 0.07 from L483 and L694-2, respectively. The detections of both CO and CH3OH for the first time through lines of sight toward background stars observationally constrains the conversion of CO into CH3OH ice. Along the lines of sight, most of the CO exists in the gas phase and ≤15% of the CO is frozen out. However, CH3OH ice is abundant with respect to CO (∼50%) and exists mainly as a CH3OH-rich CO ice layer. Only a small fraction of the lines of sight contains CH3OH ice, presumably those with the highest density. The high conversion of CO to CH3OH can explain the abundances of CH3OH ice found in later stage Class 1 low-mass YSO envelopes (CH3OH:CO r ∼ 0.5–0.6). For high-mass YSOs and one Class 0 YSO, this ratio varies significantly, implying local variations can affect ice formation. The large CH3OH ice abundance indicates that the formation of complex organic molecules is likely during the prestellar phase in cold environments without higher energy particle interactions (e.g., cosmic rays).

Synthesis and characterization of peptides after high-energy impact on the icy matrix: Preliminary step for further UV-induced formation

Quantifying the composition of the material in protoplanetary disks is essential to determining the potential for exoplanetary systems to produce and support habitable environments. When considering potential habitability, complex organic molecules are relevant, key among which is methanol (CH3OH). Methanol primarily forms at low temperatures via the hydrogenation of CO ice on the surface of icy dust grains and is a necessary basis for the formation of more complex species such as amino acids and proteins. We report the detection of CH3OH in a disk around a young, luminous A-type star, HD 100546. This disk is warm and therefore does not host an abundant reservoir of CO ice. We argue that the CH3OH cannot form in situ, and hence that this disk has probably inherited complex-organic-molecule-rich ice from an earlier cold dark cloud phase. This is strong evidence that at least some interstellar organic material survives the disk-formation process and can then be incorporated into forming planets, moons and comets. Therefore, crucial pre-biotic chemical evolution already takes place in dark star-forming clouds. The detection of methanol—a molecule that primarily forms on the cold, icy surfaces of dust grains—in a warm protoplanetary disk is an indication that complex organic molecules are inherited from the interstellar medium and transported intact to planet-forming regions.

Meteorites and their components have anomalous oxygen isotopic compositions characterized by large variations in 18O/16O and 17O/16O ratios. On the basis of recent observations of star-forming regions and models of accreting protoplanetary disks, we suggest that these variations may originate in a parent molecular cloud by ultraviolet photodissociation processes. Materials with anomalous isotopic compositions were then transported into the solar nebula by icy dust grains during the collapse of the cloud. The icy dust grains drifted toward the Sun in the disk, and their subsequent evaporation resulted in the 17O- and 18O-enrichment of the inner disk gas.

Sticking of H and D atoms on interstellar dust grains is the first step in molecular hydrogen formation, which is a key reaction in the InterStellar Medium (ISM). After studying the sticking coefficients of H2 and D2 molecules on amorphous silicate surfaces experimentally and theoretically, we extrapolate the results to the sticking coefficient of atoms and propose a formulae that gives the sticking coefficients of H and D on both silicates and icy dust grains. In our experiments, we used the King and Wells method for measuring the sticking coefficients of H2 and D2 molecules on a silicate surface held at 10 K. It consists of measuring with a QMS (quadrupole mass spectrometer) the signals of H2 and D2 molecules reflected by the surface during the exposure of the sample to the molecular beam at a temperature ranging from 20 K to 340 K. We tested the efficiency of a physical model, developed previously for sticking on water-ice surfaces. We applied this model to our experimental results for the sticking coefficients of H2 and D2 molecules on a silicate surface and estimated the sticking coefficient of atoms by a single measurement of atomic recombination and propose an extrapolation. Sticking of H, D, HD, H2, and D2 on silicates grains behaves the same as on icy dust grains. The sticking decreases with the gas temperature, and is dependent on the mass of the impactor. The sticking coefficient for both surfaces and impactors can be modeled by an analytical formulae S(T), which describes both the experiments and the thermal distribution expected in an astrophysical context. The parameters S0 and T0 are summarized in a table. Previous estimates for the sticking coefficient of H atoms are close to the new estimation; however, we find that, when isotopic effects are taken into account, the sticking coefficient variations can be as much as a factor of 2 at T=100 K.

Tracking CHNOS during the first stages of planet formation