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Photochemistry of N-Methylformamide: Matrix Isolation and Nonadiabatic Dynamics

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http://pubman.mpdl.mpg.de/cone/persons/resource/persons58496

Crespo-Otero,  Rachel
Research Group Barbatti, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons101503

Sánchez-García,  Elsa
Research Group Sánchez-García, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons58410

Barbatti,  Mario
Research Group Barbatti, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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cphc_201200573_sm_miscellaneous_information.pdf
(Supplementary material), 2MB

Citation

Crespo-Otero, R., Mardyukov, A., Sánchez-García, E., Barbatti, M., & Sander, W. (2013). Photochemistry of N-Methylformamide: Matrix Isolation and Nonadiabatic Dynamics. ChemPhysChem, 14(4), 827-836. doi:10.1002/cphc.201200573.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0014-A3D2-6
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—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.