Photochemistry of glycolaldehyde in cryogenic matrices

International audienceThe photochemistry of glycolaldehyde (GA) upon irradiation at 266 nm is investigated in argon, nitrogen, neon, and para-hydrogen matrices by IR spectroscopy. Isomerization and fragmentation processes are found to compete. The hydrogen-bonded Cis-Cis form of GA is transformed mainly to the open Trans-Trans conformer and to CO and CH3OH fragments and their mixed complexes. Different photo-induced behaviours appear depending on the matrix. In nitrogen, small amounts of Trans-Gauche and Trans-Trans conformers are detected after deposition and grow together upon irradiation. The Trans-Gauche conformer is characterized for the first time. In para-hydrogen due to a weaker cage effect additional H2CO and HCO fragments are seen. Calculations of the potential energy surfaces of S0, S1, and T1 states – to analyse the torsional deformations which are involved in the isomerization process – and a kinetic analysis are presented to investigate the different relaxation pathways of GA. Fragmentation of GA under UV irradiation through the CO+CH3OH molecular channel is a minor process, as in the gas phase

P2P Web service based system for supporting decision-making in cellular manufacturing scheduling

With the increase of the Internet and Virtual Enterprises (VEs), interfaces for web systems and automated services are becoming an emergent necessity. In this paper we propose a Peer-to-peer (P2P) web-based decision-support system for enabling access to different manufacturing scheduling methods, which can be remotely available and accessible from a distributed knowledge base. The XML-based modeling and communication is applied to manufacturing scheduling. Therefore, manufacturing scheduling problems and methods are modeled using XML. The proposed P2P web-based system works as web services, under the SOAP protocol. The system’s distributed knowledge base enables sharing information about scheduling problems and corresponding solving methods in a widened search space, through a scheduling community, integrating a VE. Running several methods enables different results for a given problem, consequently, contributing for a better decision-making. An important aspect is that this knowledge base can be easily and continuously updated by any contributor through the VE. Moreover, through this system once suitable available methods, for a given problem, are identified, it enables running one or more of them, for enabling a better manufacturing scheduling support, enhanced though incorporated fuzzy decision-making proceduresAichi Science and Technology Foundation(PTDC/EME-GIN/102143/2008)info:eu-repo/semantics/publishedVersio

Probing model interstellar grain surfaces with small molecules

Temperature-programmed desorption and reflection-absorption infrared spectroscopy have been used to explore the interaction of oxygen (O2), nitrogen (N2), carbon monoxide (CO) and water (H2O) with an amorphous silica film as a demonstration of the detailed characterization of the silicate surfaces that might be present in the interstellar medium. The simple diatomic adsorbates are found to wet the silica surface and exhibit first-order desorption kinetics in the regime up to monolayer coverage. Beyond that, they exhibit zero-order kinetics as might be expected for sublimation of bulk solids. Water, in contrast, does not wet the silica surface and exhibits zero-order desorption kinetics at all coverages consistent with the formation of an islanded structure. Kinetic parameters for use in astrophysical modelling were obtained by inversion of the experimental data at sub-monolayer coverages and by comparison with models in the multilayer regime. Spectroscopic studies in the sub-monolayer regime show that the C–O stretching mode is at around 2137 cm−1 (5.43 μm), a position consistent with a linear surface–CO interaction, and is inhomogenously broadened as resulting from the heterogeneity of the surface. These studies also reveal, for the first time, direct evidence for the thermal activation of diffusion, and hence de-wetting, of H2O on the silica surface. Astrophysical implications of these findings could account for a part of the missing oxygen budget in dense interstellar clouds, and suggest that studies of the sub-monolayer adsorption of these simple molecules might be a useful probe of surface chemistry on more complex silicate materials

Water dimer in solid neon. Far-infrared spectrum

Infrared spectra of water and deuterated water isolated in neon matrices have been recorded between 20 and 5000 cm(-1). The water concentration has been varied between very low concentrations with only monomers present up to concentrations where pentamers and possibly hexamers are present in significant amounts. The concentration dependencies of the observed absorption bands have been used to assign the dimer spectrum. The matrices studied were on the order of 1 mm thick, which has made it simpler to vary concentrations in a manner which discriminates between higher aggregates. It has also made it possible to avoid the baseline problems which appear when the matrices are only slightly thicker than the wavelengths in the far-infrared part of the spectrum

A simple model for the water o-H-2 complex

The infrared spectrum of the complex between o-H-2 and H2O, D2O, or HDO, isolated in a matrix of solid p-H-2, has been studied between 20 and 4500 cm(-1). In addition the infrared spectrum of the complex between p-D-2 and H2O in solid o-D-2 has been studied. The spectral shifts are interpreted as the result of the quadrupole-dipole interaction between hydrogen and water. (c) 2006 American Institute of Physics

Far-Infrared Band Strengths in the Water Dimer: Experiments and Calculations.

Most fundamentals modes of the water dimer have been experimentally determined, and the frequencies have been measured in either neon or parahydrogen matrices. The band strengths of all intramolecular and most intermolecular fundamentals of the water dimer have been measured. The results are further corroborated by comparison with the corresponding data for the fully deuterated water dimer. DFT calculations of the mode frequencies and band strength are in qualitative agreement with the experimental observations