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Title: Photochemistry of glycolaldehyde in cryogenic matrices

The 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 CH{sub 3}OH 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 H{sub 2}CO and HCO fragments are seen. Calculations of the potential energy surfaces of S{sub 0}, S{sub 1}, and T{sub 1} 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+CH{sub 3}OH molecular channel is a minor process, as in the gas phase.
Authors:
; ; ;  [1] ;  [2] ;  [3]
  1. Institut des Sciences Moléculaires d’Orsay, CNRS UMR 8214, Université Paris-Sud, 91405 Orsay (France)
  2. DSM/IRAMIS/SIS2M (CEA-CNRS UMR3299), Commissariat à l’Énergie Atomique, 91191 Gif-sur-Yvette (France)
  3. Department of General Physics and Spectroscopy, Vilnius University, 01315 Vilnius (Lithuania)
Publication Date:
OSTI Identifier:
22420086
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 22; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DEFORMATION; DEPOSITION; HYDROGEN; INFRARED SPECTRA; IRRADIATION; ISOMERIZATION; METHANOL; NITROGEN; POTENTIAL ENERGY