Water formation at low temperatures by surface O2 hydrogenation I: characterization of ice penetration

Water is the main component of interstellar ice mantles, is abundant in the solar system and is a crucial ingredient for life. The formation of this molecule in the interstellar medium cannot be explained by gas-phase chemistry only and its surface hydrogenation formation routes at low temperatures (O, O2, O3 channels) are still unclear and most likely incomplete. In a previous paper we discussed an unexpected zeroth-order H2O production behavior in O2 ice hydrogenation experiments compared to the first-order H2CO and CH3OH production behavior found in former studies on hydrogenation of CO ice. In this paper we experimentally investigate in detail how the structure of O2 ice leads to this rare behavior in reaction order and production yield. In our experiments H atoms are added to a thick O2 ice under fully controlled conditions, while the changes are followed by means of reflection absorption infrared spectroscopy (RAIRS). The H-atom penetration mechanism is systematically studied by varying the temperature, thickness and structure of the O2 ice. We conclude that the competition between reaction and diffusion of the H atoms into the O2 ice explains the unexpected H2O and H2O2 formation behavior. In addition, we show that the proposed O2 hydrogenation scheme is incomplete, suggesting that additional surface reactions should be considered. Indeed, the detection of newly formed O3 in the ice upon H-atom exposure proves that the O2 channel is not an isolated route. Furthermore, the addition of H2 molecules is found not to have a measurable effect on the O2 reaction channel.Comment: 1 page, 1 figur

Water formation at low temperatures by surface O2 hydrogenation II: the reaction network

Water is abundantly present in the Universe. It is the main component of interstellar ice mantles and a key ingredient for life. Water in space is mainly formed through surface reactions. Three formation routes have been proposed in the past: hydrogenation of surface O, O2, and O3. In a previous paper [Ioppolo et al., Astrophys. J., 2008, 686, 1474] we discussed an unexpected non-standard zeroth-order H2O2 production behaviour in O2 hydrogenation experiments, which suggests that the proposed reaction network is not complete, and that the reaction channels are probably more interconnected than previously thought. In this paper we aim to derive the full reaction scheme for O2 surface hydrogenation and to constrain the rates of the individual reactions. This is achieved through simultaneous H-atom and O2 deposition under ultra-high vacuum conditions for astronomically relevant temperatures. Different H/O2 ratios are used to trace different stages in the hydrogenation network. The chemical changes in the forming ice are followed by means of reflection absorption infrared spectroscopy (RAIRS). New reaction paths are revealed as compared to previous experiments. Several reaction steps prove to be much more efficient (H + O2) or less efficient (H + OH and H2 + OH) than originally thought. These are the main conclusions of this work and the extended network concluded here will have profound implications for models that describe the formation of water in space.Comment: 1 page, 1 figur

Enhanced mesoscopic fluctuations in the crossover between random matrix ensembles

In random-matrix ensembles that interpolate between the three basic ensembles (orthogonal, unitary, and symplectic), there exist correlations between elements of the same eigenvector and between different eigenvectors. We study such correlations, using a remarkable correspondence between the interpolating ensembles late in the crossover and a basic ensemble of finite size. In small metal grains or semiconductor quantum dots, the correlations between different eigenvectors lead to enhanced fluctuations of the electron-electron interaction matrix elements which become parametrically larger than the non-universal fluctuations.Comment: 4 pages, RevTeX; 3 figure

Surface formation of hcooh at low temperature

Contains fulltext : 92389.pdf (publisher's version ) (Open Access)7 p

Surface formation of co(2) ice at low temperatures

Contains fulltext : 92388.pdf (publisher's version ) (Open Access)8 p

Double K-shell excitation of Li by 10.6-MeV/nucleon N7+ projectiles

International audienceSingle and double K-shell excitation of Li by 10.6-MeV/nucleon N7+ projectiles is investigated by measuring Li autoionization spectra in the energy range from 50 to 90 eV. The ratio for double K-shell excitation to single K-shell excitation is determined to be about 0.36%. The measured ratio for double-to-single K-shell excitation of Li is about a factor of 2 larger than calculations based on independent interactions between the projectile nucleus and each of the Li target electrons, indicating that the electron-electron interaction plays a dominant role in the double K-shell excitation of Li in these collisions

Total Synthesis of Solandelactones A and B

The total synthesis of solandelactones A and B is presented. The eastern cyclopropyl moiety was prepared following an exceptionally short chemoenzymatic approach whereas enantioselective synthesis of the western side-chain relied on the application of diastereomerically pure allyl boronates. The natural products solandelactones A and B were isolated in good overall yields following convergence of each eastern and western element by application of the Nozaki–Hiyama–Kishi reaction