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 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.
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14 June 2014
Research Article|
June 13 2014
Photochemistry of glycolaldehyde in cryogenic matrices
W. Chin;
W. Chin
a)
1Institut des Sciences Moléculaires d’Orsay, CNRS UMR 8214,
Université Paris-Sud
, 91405 Orsay, France
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M. Chevalier;
M. Chevalier
1Institut des Sciences Moléculaires d’Orsay, CNRS UMR 8214,
Université Paris-Sud
, 91405 Orsay, France
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R. Thon;
R. Thon
1Institut des Sciences Moléculaires d’Orsay, CNRS UMR 8214,
Université Paris-Sud
, 91405 Orsay, France
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R. Pollet;
R. Pollet
2DSM/IRAMIS/SIS2M (CEA-CNRS UMR3299),
Commissariat à l’Énergie Atomique
, 91191 Gif-sur-Yvette, France
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J. Ceponkus;
J. Ceponkus
3Department of General Physics and Spectroscopy,
Vilnius University
, 01315 Vilnius, Lithuania
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C. Crépin
C. Crépin
1Institut des Sciences Moléculaires d’Orsay, CNRS UMR 8214,
Université Paris-Sud
, 91405 Orsay, France
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a)
Author to whom correspondence should be addressed. Electronic mail: [email protected]
J. Chem. Phys. 140, 224319 (2014)
Article history
Received:
January 28 2014
Accepted:
May 23 2014
Citation
W. Chin, M. Chevalier, R. Thon, R. Pollet, J. Ceponkus, C. Crépin; Photochemistry of glycolaldehyde in cryogenic matrices. J. Chem. Phys. 14 June 2014; 140 (22): 224319. https://doi.org/10.1063/1.4881605
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