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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See supplementary material at http://dx.doi.org/10.1063/1.4881605 for bond distances of the computed conformers of GA in the ground and excited states; complete IR spectra of GA in pH2, Ne, Ar, and N2 matrices; IR spectrum of TT and TG in N2 in the νOH bands region; IR spectrum of GA in pH2 after 110 min of irradiation at 266 nm in the CO bands region; IR bands of HCO and H2CO fragments after very long 266 nm irradiation of GA in pH2.

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