G. Fedoseev

Experimental evidence for glycolaldehyde and ethylene glycol formation by surface hydrogenation of co molecules under dense molecular cloud conditions

This study focuses on the formation of two molecules of astrobiological importance – glycolaldehyde(HC(O)CH2OH)andethyleneglycol(H2C(OH)CH2OH)–bysurfacehydrogenation of CO molecules. Our experiments aim at simulating the CO freeze-out stage in interstellar darkcloudregions,wellbeforethermalandenergeticprocessingbecomedominant.Itisshown 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.

H-atom addition and abstraction reactions in mixed CO, H2CO and CH3OH ices – an extended view on complex organic molecule formation

Complex organic molecules (COMs) have been observed not only in the hot cores surrounding low- and high- mass protostars, but also in cold dark clouds. Therefore, it is interesting to understand how such species can be formed without the presence of embedded energy sources. We present new laboratory experiments on the low-temperature solid state formation of three complex molecules: methyl formate (HC(O)OCH3), glycolaldehyde (HC(O)CH2OH) and ethylene glycol (H2C(OH)CH2OH), through recombination of free radicals formed via H-atom addition and abstraction reactions at different stages in the CO-H2CO-CH3OH hydrogenation network at 15 K. The experiments extend previous CO hydrogenation studies and aim at resembling the physical&chemical conditions typical of the CO freeze-out stage in dark molecular clouds, when H2CO and CH3OH form by recombination of accreting CO molecules and H-atoms on ice grains. We confirm that H2CO, once formed through CO hydrogenation, not only yields CH3OH through ongoing H-atom addition reactions, but is also subject to H-atom-induced abstraction reactions, yielding CO again. In a similar way, H2CO is also formed in abstraction reactions involving CH3OH. The dominant methanol H-atom abstraction product is expected to be CH2OH, while H-atom additions to H2CO should at least partially proceed through CH3O intermediate radicals. The occurrence of H-atom abstraction reactions in ice mantles leads to more reactive intermediates (HCO, CH3O and CH2OH) than previously thought, when assuming sequential H-atom addition reactions only. This enhances the probability to form COMs through radical-radical recombination without the need of UV photolysis or cosmic rays as external triggers.

Atom addition reactions in interstellar ice analogues

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.

NO ICE HYDROGENATION: A SOLID PATHWAY TO NH2OH FORMATION IN SPACE

Icy dust grains in space act as catalytic surfaces onto which complex molecules form. These molecules are synthesized through exothermic reactions from precursor radicals and, mostly, hydrogen atom additions. Among the resulting products are species of biological relevance, such as hydroxylamine—NH2OH—a precursor molecule in the formation of amino acids. In this Letter, laboratory experiments are described that demonstrate NH2OH formation in interstellar ice analogs for astronomically relevant temperatures via successive hydrogenation reactions of solid nitric oxide (NO). Inclusion of the experimental results in an astrochemical gas–grain model proves the importance of a solid-state NO + H reaction channel as a starting point for prebiotic species in dark interstellar clouds and adds a new perspective to the way molecules of biological importance may form in space.

SURFRESIDE2: An ultrahigh vacuum system for the investigation of surface reaction routes of interstellar interest

A new ultrahigh vacuum experiment is described to study atom and radical addition reactions in interstellar ice analogues for astronomically relevant temperatures. The new setup - SURFace REaction SImulation DEvice (SURFRESIDE(2)) - allows a systematic investigation of solid state pathways resulting in the formation of molecules of astrophysical interest. The implementation of a double beam line makes it possible to expose deposited ice molecules to different atoms and/or radicals sequentially or at the same time. Special efforts are made to perform experiments under fully controlled laboratory conditions, including precise atom flux determinations, in order to characterize reaction channels quantitatively. In this way, we can compare and combine different surface reaction channels with the aim to unravel the solid state processes at play in space. Results are constrained in situ by means of a Fourier transform infrared spectrometer and a quadrupole mass spectrometer using reflection absorption infrared spectroscopy and temperature programmed desorption, respectively. The performance of the new setup is demonstrated on the example of carbon dioxide formation by comparing the efficiency through two different solid state channels (CO + OH → CO2 + H and CO + O → CO2) for which different addition products are needed. The potential of SURFRESIDE(2) to study complex molecule formation, including nitrogen containing (prebiotic) compounds, is discussed.

Efficient surface formation route of interstellar hydroxylamine through NO hydrogenation. II. The multilayer regime in interstellar relevant ices

Hydroxylamine (NH(2)OH) is one of the potential precursors of complex pre-biotic species in space. Here, we present a detailed experimental study of hydroxylamine formation through nitric oxide (NO) surface hydrogenation for astronomically relevant conditions. The aim of this work is to investigate hydroxylamine formation efficiencies in polar (water-rich) and non-polar (carbon monoxide-rich) interstellar ice analogues. A complex reaction network involving both final (N(2)O, NH(2)OH) and intermediate (HNO, NH(2)O·, etc.) products is discussed. The main conclusion is that hydroxyl-amine formation takes place via a fast and barrierless mechanism and it is found to be even more abundantly formed in a water-rich environment at lower temperatures. In parallel, we experimentally verify the non-formation of hydroxylamine upon UV photolysis of NO ice at cryogenic temperatures as well as the non-detection of NC- and NCO-bond bearing species after UV processing of NO in carbon monoxide-rich ices. Our results are implemented into an astrochemical reaction model, which shows that NH(2)OH is abundant in the solid phase under dark molecular cloud conditions. Once NH(2)OH desorbs from the ice grains, it becomes available to form more complex species (e.g., glycine and β-alanine) in gas phase reaction schemes.

Low-temperature surface formation of NH3 and HNCO: hydrogenation of nitrogen atoms in CO-rich interstellar ice analogues

Solid-state astrochemical reaction pathways have the potential to link the formation of small nitrogen-bearing species, like NH_3 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 towards young stellar objects and quiescent molecular clouds. This is mainly because of the lack of dedicated laboratory studies. The aim of this work is to experimentally investigate the formation routes of NH_3 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 NH_3 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 NH_3 upon sequential hydrogenation of N atoms. The importance of HNCO for astrobiology is discussed.

Production of complex organic molecules : H-atom addition versus UV irradiation

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.

Relevance of the H2 + O reaction pathway for the surface formation of interstellar water - Combined experimental and modeling study

The formation of interstellar water has been commonly accepted to occur on the surfaces of icy dust grains in dark molecular clouds at low temperatures (10-20 K), involving hydrogenation reactions of oxygen allotropes. As a result of the large abundances of molecular hydrogen and atomic oxygen in these regions, the reaction H2 + O has been proposed to contribute significantly to the formation of water as well. However, gas phase experiments and calculations, as well as solid-phase experimental work contradict this hypothesis. Here, we use precisely executed temperature programmed desorption (TPD) experiments in an ultra-high vacuum setup combined with kinetic Monte Carlo simulations to establish an upper limit of the water production starting from H2 and O. These reactants are brought together in a matrix of CO2 in a series of (control) experiments at different temperatures and with different isotopological compositions. The amount of water detected with the quadrupole mass spectrometer upon TPD is found to originate mainly from contamination in the chamber itself. However, if water is produced in small quantities on the surface through H2 + O, this can only be explained by a combined classical and tunneled reaction mechanism. An absolutely conservative upper limit for the reaction rate is derived with a microscopic kinetic Monte Carlo model that converts the upper limit into a maximal possible reaction rate. Incorporating this rate into simulations run for astrochemically relevant parameters, shows that the upper limit to the contribution of the reaction H2 + O in OH, and hence water formation, is 11% in dense interstellar clouds. Our combined experimental and theoretical results indicate however, that this contribution is likely to be much lower.

A novel approach to measure photodesorption rates of interstellar ice analogues - The photodesorption rate of CO ice reinvestigated

Context. In recent years photodesorption rates have been determined in dedicated laboratory experiments for a number of different interstellar ice analogues. These rates are important in order to model non-thermal desorption processes that, for example, affect gas-phase abundances of species and determine the position of photo-induced snow lines in protoplanetary disks. However, different groups using similar experiments have found significant deviating photodesorption values. Aims. Here a new measurement concept is introduced that allows photodesorption rates to be determined following a different experimental approach. The potential of this method is demonstrated using the example of pure CO ice, the solid that gives the most striking discrepancies in the published results. Methods. The new experimental approach uses laser desorption post-ionisation time-of-flight mass spectrometry. It is based on the concept that the physical and geometrical properties of the plume obtained by laser induced desorption of the ice directly depend on the original ice thickness. This allows the ice loss to be determined as function of vacuum ultraviolet (VUV) fluence, which results in a photodesorption rate. The method has the additional advantage that it records all ice species, including photoproducts generated by the VUV irradiation. As a consequence, the method introduced here is also suited to determine the overall photodesorption rate of mixed ices. Results. The photodesorption rate for CO ice at 20 K has been determined as (1.4 ± 0.7) × 10 -3 molecules per incident VUV photon. This result is compared to existing experimental and theoretical values and the astronomical relevance is discussed.