Low-Energy Water-Hydrogen Inelastic Collisions.

New molecular beam scattering experiments are reported for the water-hydrogen system. Integral cross sections of the first rotational excitations of para- and ortho-H2O by inelastic collisions with normal-H2 were determined by crossing a beam of H2O seeded in He with a beam of H2. H2O and H2 were cooled in the supersonic expansion down to their lowest rotational levels. Crossed-beam scattering experiments were performed at collision energies from 15 cm-1 (below the threshold for the excitation to the lowest excited rotational state of H2O: 18.6 cm-1) up to 105 cm-1 by varying the beam crossing angle. The measured state-to-state cross-sections were compared to the theoretical cross-sections (close-coupling quantum scattering calculations): the good agreement found further validates both the employed potential energy surface describing the H2O-H2 van der Waals interaction and the state-to-state rate coefficients calculated with this potential in the very low temperature range needed for the modeling of interstellar media.

Nuclear Spin Symmetry Conservation in 1H216O Investigated by Direct Absorption FTIR Spectroscopy of Water Vapor Cooled Down in Supersonic Expansion.

We report the results of an experimental study related to the relaxation of the nuclear spin isomers of the water molecule in a supersonic expansion. Rovibrational lines of both ortho and para spin isomers were recorded in the spectral range of H2O stretching vibrations at around 3700 cm-1 using FTIR direct absorption. Water vapor seeded in argon, helium, or oxygen or in a mixture of oxygen and argon was expanded into vacuum through a slit nozzle. The water vapor partial pressure in the mixture varied over a wide range from 1.5 to 102.7 hPa, corresponding to a water molar fraction varying between 0.2 and 6.5%. Depending on expansion conditions, the effect of water vapor clustering was clearly seen in some of our measured spectra. The Boltzmann plot of the line intensities allowed the H2O rotational temperatures in the isentropic core and in the lateral shear layer probed zones of the planar expansion to be determined. The study of the OPR, i.e., the ratio of the ortho to para absorption line intensities as a function of Trot, did not reveal any signs of the OPR being relaxed to the sample temperature. In contrast, the OPR was always conserved according to the stagnation reservoir equilibrium temperature. The conservation of the OPR was found irrespective of whether water molecule clustering was pronounced or not. Also, no effect of the paramagnetic oxygen admixture enhancing OPR relaxation was observed.

Gas-phase kinetics of the N + C2N reaction at low temperature.

The rate of the gas-phase N((4)S) + C2N(X(2)Πi) reaction has been measured in a continuous supersonic flow reactor down to 54 K through the relative-rate method using the N((4)S) + OH(X(2)Π) → H((2)S) + NO(X(2)Π) reaction as a reference. The microwave discharge technique was employed to produce high concentrations of atomic nitrogen. Pulsed laser photolysis of precursor molecules Cl3C2N and H2O2 at 212 nm in situ led to C2N and OH radical formation, respectively. The rate constant is shown to be approximately independent of temperature, in contrast to previous studies of atom-radical reactions involving atomic nitrogen. While the reaction rate is faster than previously estimated, astrochemical simulations indicate that this reaction is probably only a minor source of CN radicals in dense interstellar clouds.

UV photodesorption of interstellar CO ice analogues: from subsurface excitation to surface desorption.

Carbon monoxide is after H(2) the most abundant molecule identified in the interstellar medium (ISM), and is used as a major tracer for the gas phase physical conditions. Accreted at the surface of water-rich icy grains, CO is considered to be the starting point of a complex organic--presumably prebiotic--chemistry. Non-thermal desorption processes, and especially photodesorption by UV photons, are seen as the main cause that drives the gas-to-ice CO balance in the colder parts of the ISM. The process is known to be efficient and wavelength-dependent, but, the underlying mechanism and the physical-chemical parameters governing the photodesorption are still largely unknown. Using monochromatized photons from a synchrotron beamline, we reveal that the molecular mechanism responsible for CO photoejection is an indirect, (sub)surface-located process. The local environment of the molecules plays a key role in the photodesorption efficiency, and is quenched by at least an order of magnitude for CO interacting with a water ice surface.

Vibration-rotation pattern in acetylene. II. Introduction of Coriolis coupling in the global model and analysis of emission spectra of hot acetylene around 3 microm.

A high temperature source has been developed and coupled to a high resolution Fourier transform spectrometer to record emission spectra of acetylene around 3 mum up to 1455 K under Doppler limited resolution (0.015 cm(-1)). The nu(3)-ground state (GS) and nu(2)+nu(4)+nu(5) (Sigma(u) (+) and Delta(u))-GS bands and 76 related hot bands, counting e and f parities separately, are assigned using semiautomatic methods based on a global model to reproduce all related vibration-rotation states. Significantly higher J-values than previously reported are observed for 40 known substates while 37 new e or f vibrational substates, up to about 6000 cm(-1), are identified and characterized by vibration-rotation parameters. The 3 811 new or improved data resulting from the analysis are merged into the database presented by Robert et al. [Mol. Phys. 106, 2581 (2008)], now including 15 562 lines accessing vibrational states up to 8600 cm(-1). A global model, updated as compared to the one in the previous paper, allows all lines in the database to be simultaneously fitted, successfully. The updates are discussed taking into account, in particular, the systematic inclusion of Coriolis interaction.

Efficient diffusive mechanisms of O atoms at very low temperatures on surfaces of astrophysical interest.

At the low temperatures of interstellar dust grains, it is well established that surface chemistry proceeds via diffusive mechanisms of H atoms weakly bound (physisorbed) to the surface. Until recently, however, it was unknown whether atoms heavier than hydrogen could diffuse rapidly enough on interstellar grains to react with other accreted species. In addition, models still require simple reduction as well as oxidation reactions to occur on grains to explain the abundances of various molecules. In this paper we investigate O-atom diffusion and reactivity on a variety of astrophysically relevant surfaces (water ice of three different morphologies, silicate, and graphite) in the 6.5-25 K temperature range. Experimental values were used to derive a diffusion law that emphasizes that O atoms diffuse by quantum mechanical tunnelling at temperatures as low as 6.5 K. The rates of diffusion on each surface, based on modelling results, were calculated and an empirical law is given as a function of the surface temperature. The relative diffusion rates are k(H2Oice) > k(sil) > k(graph) >> k(expected). The implications of efficient O-atom diffusion over astrophysically relevant time-scales are discussed. Our findings show that O atoms can scan any available reaction partners (e.g., either another H atom, if available, or a surface radical like O or OH) at a faster rate than that of accretion. Also, as dense clouds mature, H2 becomes far more abundant than H and the O : H ratio grows, and the reactivity of O atoms on grains is such that O becomes one of the dominant reactive partners together with H.

How micron-sized dust particles determine the chemistry of our Universe.

In the environments where stars and planets form, about one percent of the mass is in the form of micro-meter sized particles known as dust. However small and insignificant these dust grains may seem, they are responsible for the production of the simplest (H(2)) to the most complex (amino-acids) molecules observed in our Universe. Dust particles are recognized as powerful nano-factories that produce chemical species. However, the mechanism that converts species on dust to gas species remains elusive. Here we report experimental evidence that species forming on interstellar dust analogs can be directly released into the gas. This process, entitled chemical desorption (fig. 1), can dominate over the chemistry due to the gas phase by more than ten orders of magnitude. It also determines which species remain on the surface and are available to participate in the subsequent complex chemistry that forms the molecules necessary for the emergence of life.