Photofragmentation dynamics of <i>N</i>,<i>N</i>-dimethylformamide following excitation at 193 nm

  • M. Laura Lipciuc
    University of Oxford 1 Department of Chemistry, Chemistry Research Laboratory, , 12 Mansfield Road, Oxford OX1 3TA, United Kingdom
  • Sara H. Gardiner
    University of Oxford 1 Department of Chemistry, Chemistry Research Laboratory, , 12 Mansfield Road, Oxford OX1 3TA, United Kingdom
  • Tolga N. V. Karsili
    University of Bristol 2 School of Chemistry, , Cantocks Close, Bristol BS8 1TS, United Kingdom
  • Jason W. L. Lee
    University of Oxford 1 Department of Chemistry, Chemistry Research Laboratory, , 12 Mansfield Road, Oxford OX1 3TA, United Kingdom
  • David Heathcote
    University of Oxford 1 Department of Chemistry, Chemistry Research Laboratory, , 12 Mansfield Road, Oxford OX1 3TA, United Kingdom
  • Michael N. R. Ashfold
    University of Bristol 2 School of Chemistry, , Cantocks Close, Bristol BS8 1TS, United Kingdom
  • Claire Vallance
    University of Oxford 1 Department of Chemistry, Chemistry Research Laboratory, , 12 Mansfield Road, Oxford OX1 3TA, United Kingdom

書誌事項

公開日
2017-05-26
DOI
  • 10.1063/1.4983704
公開者
AIP Publishing

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説明

<jats:p>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.</jats:p>

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