Electronic state influence on selective bond breaking of core-excited nitrosyl chloride (ClNO)

The potential for selective bond breaking of a small molecule was investigated with electron spectroscopy and electron-ion coincidence experiments on ClNO. The electron spectra were measured upon direct valence photoionization and resonant core excitation at the N 1s- and O 1s-edges, followed by the emission of resonant-Auger (RA) electrons. The RA spectra were analyzed with particular emphasis on the assignment of the participator and spectator states. The states are of special relevance for investigating how distinct electronic configurations influence selective bond breaking. The electron-ion coincidence measurements provided branching fractions of the produced ion fragments as a function of electron binding energy. They explicitly demonstrate how the final electronic states created after photoionization and RA decay influence fragmentation. In particular, we observed a significantly different branching fraction for spectator states compared with participator states. In addition, it was also observed that the bonds broken for the spectator states correlate with the antibonding nature of the spectator-electron orbital. Published under an exclusive license by AIP Publishing.

Automated summary

The potential for selective bond breaking of ClNO was investigated using electron spectroscopy and electron-ion coincidence experiments. The experimental results showed that the electron-ion coincidences produced specific spectator and participator states, with significantly different branching fractions for the spectator states compared to the participator states. It was also observed that the bonds broken for the spectator states correlated with the antibonding nature of the spectator-electron orbital.