Selective dissociation of the spectator Auger final states in O2 molecules

Abstract

Molecular cationic states with two valence holes and one $n$-Rydberg electron can be created after spectator Auger decay. Unraveling these states' dissociation is often very challenging due to the frequent occurrence of conical intersections between cationic potential energy curves. Here, based on an advanced analysis of the experimental multicoincidence data obtained after $\mathrm{O}1s$ core excitation in ${\mathrm{O}}_{2}$, we achieved an energy-resolution better than we recently exploited in Phys. Rev. A 99, 022511 (2019). We therefore revealed a group of weak channels in the two-dimensional energy-correlation map between the coincident resonant Auger electron and ion in addition to the previously reported strong ones. The fragments in the identified weak channels contain only outmost electrons in valence orbitals; in contrast, the fragments in the strong channels contain an outmost electron in a ${n}^{\ensuremath{'}}$-Rydberg orbital. Compared with the strong channels, the weak channels preferentially occur at smaller principal quantum number $n$. It indicates that the electron orbital size tends to be conserved during the dissociation process. These weak features are suggested to be created by the Rydberg-valence mixing between the molecular spectator Auger final state and the very dissociative molecular cationic states without the Rydberg electron. A tendency to orbital selection is also suggested in the Rydberg-valence mixing.