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Photochemistry of N-Methylformamide: Matrix Isolation and Nonadiabatic Dynamics

Authors

  • Dr. Rachel Crespo-Otero,

    1. Department of Theory, Max Planck Institute for Coal Research, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) (0)208/306-2980
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  • Dr. Artur Mardyukov,

    1. Lehrstuhl für Organische Chemie II, Ruhr Universität Bochum, Universitätsstraße 150 44801 Bochum (Germany), Fax: (+49) (0)234-3214353
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  • Dr. Elsa Sanchez-Garcia,

    1. Department of Theory, Max Planck Institute for Coal Research, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) (0)208/306-2980
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  • Dr. Mario Barbatti,

    Corresponding author
    1. Department of Theory, Max Planck Institute for Coal Research, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) (0)208/306-2980
    • Department of Theory, Max Planck Institute for Coal Research, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) (0)208/306-2980
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  • Prof.Dr. Wolfram Sander

    Corresponding author
    1. Lehrstuhl für Organische Chemie II, Ruhr Universität Bochum, Universitätsstraße 150 44801 Bochum (Germany), Fax: (+49) (0)234-3214353
    • Lehrstuhl für Organische Chemie II, Ruhr Universität Bochum, Universitätsstraße 150 44801 Bochum (Germany), Fax: (+49) (0)234-3214353
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Abstract

The photochemistry of N-methylformamide (MF) is elucidated by investigating its photodissociation products generated by UV irradiation (248 nm) in an argon matrix (10 K). We find that, starting from trans-MF, prolonged irradiation produces cis-MF, CH3NH2 and CO fragments as major products. Another photoproduct is identified as methylformimidic acid (FIA). Nonadiabatic dynamics simulations starting from both MF conformers revealed that the internal conversion occurs within 1 ps through a C[BOND]N dissociation channel. The major product is a weakly bound complex between CH3NH and HCO radicals. This complex owes its existence to the cage effect of the matrix which allows for H-transfer reactions and recombination. By identifying the primary photoisomerization and photodissociation pathways of MF, we gain new insights into the photochemistry of peptide bonds in general, which is a prerequisite for a better understanding of the effect of UV irradiation on living systems.

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