Disentangling Multiphoton Ionization and Dissociation Channels in Molecular Oxygen Using Photoelectron–Photoion Coincidence Imaging

[Image: see text] Multiphoton excitation of molecular oxygen in the 392–408 nm region is studied using a tunable femtosecond laser coupled with a double velocity map imaging photoelectron–photoion coincidence spectrometer. The laser intensity is held at ≤∼1 TW/cm(2) to ensure excitation in the perturbative regime, where the possibility of resonance enhanced multiphoton ionization (REMPI) can be investigated. O(2)(+) production is found to be resonance enhanced around 400 nm via three-photon excitation to the e′(3)Δ(u)(v = 0) state, similar to results from REMPI studies using nanosecond dye lasers. O(+) production reaches 7% of the total ion yield around 405 nm due to two processes: autoionization following five-photon excitation of O(2), producing O(2)(+)(X(v)) in a wide range of vibrational states followed by two- or three-photon dissociation, or six-photon excitation to a superexcited O(2)** state followed by neutral dissociation and subsequent ionization of the electronically excited O atom. Coincidence detection is shown to be crucial in identifying these competing pathways.