A new multi-beam apparatus for the study of surface chemistry routes to formation of complex organic molecules in space.

A multi-beam ultra-high vacuum apparatus is presented. In this article, we describe the design and construction of a new laboratory astrophysics experiment-VErs de NoUvelles Synthèses (VENUS)-that recreates the solid-state non-energetic formation conditions of complex organic molecules in dark clouds and circumstellar environments. The novel implementation of four operational differentially pumped beam lines will be used to determine the feasibility and the rates for the various reactions that contribute to formation of molecules containing more than six atoms. Data are collected by means of Fourier transform infrared spectroscopy and quadrupole mass spectrometry. The gold-coated sample holder reaches temperatures between 7 K and 400 K. The apparatus was carefully calibrated and the acquisition system was developed to ensure that experimental parameters are recorded as accurately as possible. A great effort has been made to have the beam lines converge toward the sample. Experiments have been developed to check the beam alignment using reacting systems of neutral species (NH3 and H2CO). Preliminary original results were obtained for the {NO + H} system, which shows that chemistry occurs only in the very first outer layer of the deposited species, that is, the chemical layer and the physical layer coincide. This article illustrates the characteristics, performance, and future potential of the new apparatus in view of the forthcoming launch of the James Webb Space Telescope. We show that VENUS will have a major impact through its contributions to surface science and astrochemistry.

Quantum tunneling of oxygen atoms on very cold surfaces.

Any evolving system can change 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 submonolayer surface coverages. We derive the diffusion temperature law and observe the transition from quantum to classical diffusion. Despite 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.

Water formation through O2 + D pathway on cold silicate and amorphous water ice surfaces of interstellar interest.

The formation of the first monolayer of water molecules on bare dust grains is of primary importance to understand the growth of the icy mantles that cover dust in the interstellar medium. In this work, we explore experimentally the formation of water molecules from O(2) + D reaction on bare silicate surfaces that simulates the grains present in the diffuse interstellar clouds at visual extinctions (A(V) < 3 mag). For comparison, we also study the formation of water molecules on surfaces covered with amorphous water ice representing the dense clouds (A(V) ≥ 3 mag). Our studies focus on the formation of water molecules in the sub-monolayer and monolayer regimes using reflection absorption infrared spectroscopy and temperature-programmed desorption techniques. We provide the fractions of the products, such as D(2)O and D(2)O(2) molecules formed on three astrophysically relevant surfaces held at 10 K (amorphous olivine-type silicate, porous amorphous water ice, and nonporous amorphous water ice). Our results showed that the formation of D(2)O molecules occurs with an efficiency of about 55%-60% on nonporous amorphous water ice and about 18% on bare silicate grains surfaces. We explain the low efficiency of D(2)O water formation on the silicate surfaces by the desorption upon formation of certain products once the reaction occurs between O(2) and D atoms on the surface. A kinetic model taking into account the chemical desorption of newly formed water supports our conclusions.

Efficient surface formation route of interstellar hydroxylamine through NO hydrogenation. I. The submonolayer regime on interstellar relevant substrates.

Dust grains in the interstellar medium are known to serve as the first chemical laboratory where the rich inventory of interstellar molecules are synthesized. Here we present a study of the formation of hydroxylamine--NH(2)OH--via the non-energetic route NO + H (D) on crystalline H(2)O and amorphous silicate under conditions relevant to interstellar dense clouds. Formation of nitrous oxide (N(2)O) and water (H(2)O, D(2)O) is also observed and the reaction network is discussed. Hydroxylamine and water results are detected in temperature-programmed desorption (TPD) experiments, while N(2)O is detected by both reflection-absorption IR spectroscopy and TPD techniques. The solid state NO + H reaction channel proves to be a very efficient pathway to NH(2)OH formation in space and may be a potential starting point for prebiotic species in dark interstellar clouds. The present findings are an important step forward in understanding the inclusion of interstellar nitrogen into a non-volatile aminated species since NH(2)OH provides a solid state nitrogen reservoir along the whole evolutionary process of interstellar ices from dark clouds to planetary systems.

Translational energy and state resolved observations of D and D2 thermally desorbing from D clusters chemisorbed on graphite.

Direct D atom desorption, as well as associative desorption of D(2) molecules are observed in thermal desorption from D atoms chemisorbed on a C(0001) surface by combining laser induced T-jumps with resonance enhanced multiphoton ionization detection. Bleaching curves suggest that different classes of chemisorbed D atom clusters are present on the initial surface. The energy resolved atomic desorption flux, obtained via time of flight techniques, compares favorably (via detailed balance) with theoretical calculations of atomic sticking. Density functional theory calculations of chemical processes (atomic desorption, atomic diffusion/cluster annealing, and associative desorption) on an extensive set of four atom H(D) clusters chemisorbed on C(0001) provide a good interpretation of the experiments. State and energy resolved D(2) desorption fluxes are compared with previous state averaged results. In combination with density functional theory calculations these measurements reveal a substantial energy loss (>1 eV) to the surface in the associative desorption.

High translational energy release in H2 (D2) associative desorption from H (D) chemisorbed on C(0001).

Highly energetic translational energy distributions are reported for hydrogen and deuterium molecules desorbing associatively from the atomic chemisorption states on highly oriented pyrolytic graphite (HOPG). Laser assisted associative desorption is used to measure the time of flight of molecules desorbing from a hydrogen (deuterium) saturated HOPG surface produced by atomic exposure from a thermal atom source at around 2100 K. The translational energy distributions normal to the surface are very broad, from approximately 0.5 to approximately 3 eV, with a peak at approximately 1.3 eV. The highest translational energy measured is close to the theoretically predicted barrier height. The angular distribution of the desorbing molecules is sharply peaked along the surface normal and is consistent with thermal broadening contributing to energy release parallel to the surface. All results are in qualitative agreement with recent density functional theory calculations suggesting a lowest energy para-type dimer recombination path.

Interaction of D2 with H2O amorphous ice studied by temperature-programmed desorption experiments.

The gas-surface interaction of molecular hydrogen D2 with a thin film of porous amorphous solid water (ASW) grown at 10 K by slow vapor deposition has been studied by temperature-programmed-desorption (TPD) experiments. Molecular hydrogen diffuses rapidly into the porous network of the ice. The D2 desorption occurring between 10 and 30 K is considered here as a good probe of the effective surface of ASW interacting with the gas. The desorption kinetics have been systematically measured at various coverages. A careful analysis based on the Arrhenius plot method has provided the D2 binding energies as a function of the coverage. Asymmetric and broad distributions of binding energies were found, with a maximum population peaking at low energy. We propose a model for the desorption kinetics that assumes a complete thermal equilibrium of the molecules with the ice film. The sample is characterized by a distribution of adsorption sites that are filled according to a Fermi-Dirac statistic law. The TPD curves can be simulated and fitted to provide the parameters describing the distribution of the molecules as a function of their binding energy. This approach contributes to a correct description of the interaction of molecular hydrogen with the surface of possibly porous grain mantles in the interstellar medium.