Distinguishing resonance symmetries with energy-resolved photoion angular distributions from ion-pair formation in O2 following two-photon absorption of a 9.3 eV femtosecond pulse.

ABSTRACT

We present a combined experimental and theoretical study on the photodissociation dynamics of ion-pair formation in O2 following resonant two-photon absorption of a 9.3 eV femtosecond pulse, where the resulting O+ ions are detected using 3D momentum imaging. Ion-pair formation states of Σg-3 and 3Πg symmetry are accessed through predissociation of optically dark continuum Rydberg states converging to the B Σg-2 ionic state, which are resonantly populated via a mixture of both parallel-parallel and parallel-perpendicular two-photon transitions. This mixture is evident in the angular distribution of the dissociation relative to the light polarization and varies with the kinetic energy release (KER) of the fragmenting ion pair. The KER-dependent photoion angular distribution reveals the underlying two-photon absorption dynamics involved in the ion-pair production mechanism and indicates the existence of two nearly degenerate continuum resonances possessing different symmetries, which can decay by coupling to ion-pair states of the same total symmetry through internal conversion.