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Photofragmentation dynamics of N,N-dimethylformamide following excitation at 193 nm

Research output: Contribution to journalArticle

Original languageEnglish
Article number013941
Number of pages11
JournalJournal of Chemical Physics
Issue number1
Early online date26 May 2017
DateAccepted/In press - 1 May 2017
DateE-pub ahead of print - 26 May 2017
DatePublished (current) - 7 Jul 2017


N,N-dimethylformamide, HCON(CH3)2, is a useful model compound for investigating the peptide bond photofragmentation dynamics. We report data from a comprehensive experimental and theoretical study into the photofragmentation dynamics of N,N-dimethylformamide in the gas phase at 193 nm. Through a combination of velocity-map imaging and hydrogen atom Rydberg tagging photofragment translational spectroscopy we have identified two primary fragmentation channels, namely, fission of the N–CO “peptide” bond and N–CH3 bond fission leading to the loss of CH3. The possible fragmentation channels leading to the observed products are rationalised with recourse to CASPT2 calculations of the ground and first few excited-state potential energy curves along the relevant dissociation coordinates, and the results are compared with the data from previous experimental and theoretical studies on the same system.

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