Dissociative photoionisation of O₂ with tunable 10, 20 and 30 eV photons

Atomic oxygen ions, O+, created by photoexcitation of a cold supersonic beam of O2 by the output of a free-electron laser operating in the 128–122 nm region are detected by sliced velocity map imaging. Analysis of the richly structured high resolution kinetic energy and angular distributions obtained show that O+ production is due to the second and third harmonics present in the laser output. Excellent slicing and optimal velocity mapping allows separation of overlapping signal from dissociative photoionisation processes driven by 20 eV versus 30 eV photons. A two-colour experiment combining the free electron laser and a nanosecond dye laser output at 225.6 nm allowed detection of direct photodissociation of the metastable O2 + b4Σg- (v = 0–4) state is observed and assigned to a parallel b4Σg- – (c4Σu-)4s Rydberg transition followed by dissociation to O+ (4S) + O(3P2).