N-NO & NN-O bond cleavage dynamics in two- and three-body Coulomb explosion of the NO dication.

Triatomic Coulomb explosion dynamics are initiated by single-photon double ionization of NO with an ultrafast EUV pulse and are probed by delayed near-IR pulses. The triatomic benchmark system exhibits competing two- and three-body dissociation dynamics that are reflected in the time resolved branching ratios and in the co-linear three-body momentum correlation spectra. Both the N-NO and the NN-O bond dissociation channels result in vibrationally excited molecular products. Channel resolved kinetic energy release (KER) spectra exhibit shifts emerging at long probe delays of hundreds of femtoseconds. The asymptotic shifts, towards lower KER indicate that the long-range Coulomb repulsion is effectively screened at bond-distances above ∼16 Å, at which the Rydberg electron is localized on one of the dissociating fragments. Thus, revealing up to a 0.9 eV gap that develops between the molecular Rydberg ion state and its core at long bond distance.