Dissociative photoionization of NO across a shape resonance in the XUV range using circularly polarized synchrotron radiation.

Abstract

We report benchmark results for dissociative photoionization (DPI) spectroscopy and dynamics of the NO molecule in the region of the σ* shape resonance in the ionization leading to the NO+(c3Π) ionic state. The experimental study combines well characterized extreme ultraviolet (XUV) circularly polarized synchrotron radiation, delivered at the DESIRS beamline (SOLEIL), with ion-electron coincidence 3D momentum spectroscopy. The measured (N+, e) kinetic energy correlation diagrams reported at four discrete photon energies in the extended 23-33 eV energy range allow for resolving the different active DPI reactions and underline the importance of spectrally resolved studies using synchrotron radiation in the context of time-resolved studies where photoionization is induced by broadband XUV attosecond pulses. In the dominant DPI reaction which leads to the NO+(c3Π) ionic state, photoionization dynamics across the σ* shape resonance are probed by molecular frame photoelectron angular distributions where the parallel and perpendicular transitions are highlighted, as well as the circular dichroism CDAD(θe) in the molecular frame. The latter also constitute benchmark references for molecular polarimetry. The measured dynamical parameters are well described by multichannel Schwinger configuration interaction calculations. Similar results are obtained for the DPI spectroscopy of highly excited NO+ electronic states populated in the explored XUV photon energy range.