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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.

Significance Formation of clathrate hydrate (CH) requires high pressures and moderate temperatures, which enable their existence in marine sediments and the permafrost region of earth. The presence of CHs in interstellar medium (ISM) is still in question due to the extreme high vacuum and ultracold conditions present there. Here, we conclusively identified methane and carbon dioxide hydrates in conditions analogous to ISM. We found that molecular mobility and interactions play crucial roles in the formation of CHs, even though there is no external pressure to force cage formation. Various chemical processes on these hydrates in ISM may lead to relevant prebiotic molecules., Clathrate hydrates (CHs) are ubiquitous in earth under high-pressure conditions, but their existence in the interstellar medium (ISM) remains unknown. Here, we report experimental observations of the formation of methane and carbon dioxide hydrates in an environment analogous to ISM. Thermal treatment of solid methane and carbon dioxide–water mixture in ultrahigh vacuum of the order of 10−10 mbar for extended periods led to the formation of CHs at 30 and 10 K, respectively. High molecular mobility and H bonding play important roles in the entrapment of gases in the in situ formed 512 CH cages. This finding implies that CHs can exist in extreme low-pressure environments present in the ISM. These hydrates in ISM, subjected to various chemical processes, may act as sources for relevant prebiotic molecules.

The formation of molecules in and on amorphous solid water (ASW) as it occurs in interstellar space releases appreciable amounts of energy that need to be dissipated to the environment. Here, energy transfer between CO$_2$ formed within and on the surface of amorphous solid water (ASW) and the surrounding water is studied. Following CO($^1 \Sigma^+$) + O($^1$D) recombination the average translational and internal energy of the water molecules increases on the $\sim 10$ ps time scale by 15 % to 20 % depending on whether the reaction takes place on the surface or in an internal cavity of ASW. Due to tight coupling between CO$_2$ and the surrounding water molecules the internal energy exhibits a peak at early times which is present for recombination on the surface but absent for the process inside ASW. Energy transfer to the water molecules is characterized by a rapid $\sim 10$ ps and a considerably slower $\sim 1$ ns component. Within 50 ps a mostly uniform temperature increase of the ASW across the entire surface is found. The results suggest that energy transfer between a molecule formed on and within ASW is efficient and helps to stabilize the products generated., Comment: 25 pages

We report new computational and experimental evidence of an efficient and astrochemically relevant formation route to formaldehyde (H$_2$CO). This simplest carbonylic compound is central to the formation of complex organics in cold interstellar clouds, and is generally regarded to be formed by the hydrogenation of solid-state carbon monoxide. We demonstrate H$_2$CO formation via the reaction of carbon atoms with amorphous solid water. Crucial to our proposed mechanism is a concerted proton transfer catalyzed by the water hydrogen bonding network. Consequently, the reactions $^3$C + H$_2$O -> $^3$HCOH and $^1$HCOH -> $^1$H$_2$CO can take place with low or without barriers, contrary to the high-barrier traditional internal hydrogen migration. These low barriers or absence thereof explain the very small kinetic isotope effect in our experiments when comparing the formation of H$_2$CO to D$_2$CO. Our results reconcile the disagreement found in the literature on the reaction route: C + H$_2$O -> H$_2$CO., Accepted for publication in JPCL

Photodesorption of CO is suggested as a possible process which maintains a measurable amount of gaseous CO in cold interstellar clouds. In this study, the 157 nm photodesorption of CO(v = 0) adsorbed on amorphous solid water and polycrystalline ice were investigated at 8–170 K. Photodesorbed CO(v = 0) was detected by (2+1) resonance enhanced multiphoton ionization technique. Time-of-flight spectra of CO(v = 0) reveal the translational energy distributions, from which the possibility of three photodesorption processes are deduced. When the temperature is increased, photodesorption of CO(v = 0) shows four peaks at around 20–30 K, 40–60 K, 65–75 K, and 145–160 K, which are due to CO-bonded OH, CO-dangling OH, structural change from high density to low density amorphous ice, and H2O desorption, respectively.

The phase conversion of amorphous solid water (ASW) to crystalline ice (CI) has been investigated in the very thin ( ∼ 10 monolayers) film regime on a Ru(0 0 1) surface. We analyze the converted CI fraction with the Avrami model, and recognize that one-dimensional CI growth occurs, which can be contrasted to the three-dimensional CI growth generally established in the thick ( ≥ 50 monolayers) film regime. We evaluate activation energy for the ASW crystallization to be about 1.0 eV. We suggest that the ASW crystallization is not influenced by the substrate even near the substrate–ice interface.

Electron-stimulated oxidation of CO in layered H2O/CO/H2O ices was investigated with infrared reflectionabsorption spectroscopy (IRAS) as a function of the distance of the CO layer from the water/vacuum interface. The results show that while both oxidation and reduction reactions occur within the irradiated water films, there are distinct regions where either oxidation or reduction reactions are dominant. At depths less than similar to 15 ML from the vacuum interface, CO oxidation to CO2 dominates over the sequential hydrogenation of CO to methanol (CH3OH), consistent with previous observations. At its highest yield, CO2 accounts for similar to 45% of all the reacted CO. Another oxidation product is identified as the formate anion (HCO2). In contrast, for CO buried more than similar to 35 ML below the water/vacuum interface, the CO-to-methanol conversion efficiency is close to 100%. Production of CO2 and formate is not observed for the more deeply buried CO layers, where hydrogenation dominates. Experiments with CO dosed on preirradiated ASW samples suggest that OH radicals are primarily responsible for the oxidation reactions. Possible mechanisms of CO oxidation, involving primary and secondary processes of water radiolysis at low temperature, are discussed. The observed distance-dependent radiation chemistry results from the higher mobility of hydrogen atoms that are created by the interaction of the 100 eV electrons with the water films. These hydrogen atoms, which are primarily created at or near the water/vacuum interface, can desorb from or diffuse into the water films, while the less-mobile OH radicals remain in the near-surface zone, resulting in preferential oxidation reactions there. The diffusing hydrogen atoms are responsible for the hydrogenation reactions that are dominant for the more deeply buried CO layers.

Low-energy (100 eV) electron-stimulated reactions in layered H 2O/CO/H2O ices are investigated. For CO layers buried in amorphous solid water (ASW) films at depths of 50 monolayers (ML) or less from the vacuum interface, both oxidation and reduction reactions are observed. However, for CO buried more deeply in ASW films, only the reduction of CO to methanol is observed. Experiments with layered films of H2O and D2O show that the hydrogen atoms participating in the reduction of the buried CO originate in the region that is 10-50 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried CO layers, the CO reduction reactions quickly increase with temperature above ∼60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol to account for the observations. © 2014 AIP Publishing LLC.

Any evolving system can change of state via thermal mechanisms (hopping a barrier) or via quantum tunneling. Most of the time, efficient classical mechanisms dominate at high temperatures. This is why an increase of the temperature can initiate the chemistry. We present here an experimental investigation of O-atom diffusion and reactivity on water ice. We explore the 6-25 K temperature range at sub-monolayer surface coverages. We derive the diffusion temperature law and observe the transition from quantum to classical diffusion. Despite of the high mass of O, quantum tunneling is efficient even at 6 K. As a consequence, the solid-state astrochemistry of cold regions should be reconsidered and should include the possibility of forming larger organic molecules than previously expected., Comment: 13 pages, 4 figures

International audience; First results are reported on overtone (v(OH) = 2

We have investigated the interaction of n-butanol (NBA) with thin layers of water ice prepared in ultra high vacuum in the temperature range of 110-150 K. From the mass spectra of the chemically sputtered species, created upon the collision of low energy (?30 eV) Ar + ions, we study the process of diffusive mixing of NBA with water ice, at the molecular level. The results show that NBA undergoes diffusive mixing with H 2O. Even after depositing 1000 monolayers (MLs) of amorphous solid water (ASW) over NBA, both the species are observed on the surface. However, when NBA is deposited over ASW, no water is seen on the surface above 3-5 MLs of NBA. This could be interpreted as the absence of diffusive mixing in this system or surface segregation of NBA, in view of its lower surface energy just as in the case of liquid alcohols. An isomeric alcohol, namely, tert-butyl alcohol (TBA), also behaves similarly. Although the presence of NBA and TBA is detected, in the presence of ASW, they undergo selective ionization, giving specific peaks in the mass spectrum. D 2O behaves in a manner similar to that of H 2O. Preliminary experiments with other alcohols; namely, methanol, ethanol, and propanol were also done, and the results suggest that incomplete diffusion or surface segregation begins with propanol. � 2009 American Chemical Society.

We report simulated infrared (IR) spectra of deuterated water and ice using Car-Parrinello molecular dynamics with maximally localized Wannier functions. Experimental features are accurately reproduced within the harmonic approximation. By decomposing the line shapes in terms of intramolecular and intermolecular dipole correlation functions, we find that short-range intermolecular dynamic charge fluctuations associated to hydrogen bonds are prominent over the entire spectral range. Our analysis reveals the origin of several spectral features and identifies network bending modes in the far IR range.

The thesis "Light-induced molecular processes on ice" deals with two main issues: first, the interaction of water with a platinum surface, under very well-defined conditions (at liquid nitrogen temperature in a very low-pressure environment (Ultra-High Vacuum: pressure 2 x 10-11 mbar)), and second, the photochemistry of small, naturally occurring, organic molecules such as bromoform (CHBr3) molecules on ice surfaces. The first topic is of relevance for electrochemistry, where water-metal interactions are crucial in determining the system's reactivity. The second topic is relevant for our understanding of processes encountered in the Earth's atmosphere. In particular, for atmospheric chemistry, the fundamental steps of the photochemical reaction of bromoform on ice surfaces induced by UV light, are elucidated. This reaction constitutes an important step in the ozone depletion cycle, which greatly affects our atmosphere. Photodissociation studies reveal a rich UV-induced photochemistry of bromoform on ice: various direct fragmentation pathways, as well as formation of new, ice-mediated C—C and C—O bond containing chemical species. Given the previously reported detection of bromoform in the stratosphere, these observations may have significant implications for current models describing stratospheric ozone depletion.