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.