Breakdown of dipole Born approximation and the role of Rydberg's predissociation for the electron-induced ion-pair dissociation to oxygen in the presence of background gases.

We study the electron-induced ion-pair dissociation to gas-phase oxygen molecules using a state-of-the-art velocity-map ion-imaging technique. The analysis is entirely based on the conical time-gated wedge-shaped velocity slice images of O-/O2 nascent anionic fragments, and the resulting observations are in favor of Van Brunt et al.'s report [R. J. Van Brunt and L. J. Kieffer, J. Chem. Phys. 60, 3057 (1974)]. A new image reconstruction method, Jacobian over parallel slicing, is introduced to overcome the drawback of ion exaggeration in determining the kinetic energy distribution from the time-gated parallel slicing technique, which offers an alternative approach to the wedge slicing method. Most importantly, the role of the quintet-heavy Rydberg state has been drawn out to the complex ion-pair formalism. The extracted kinetic energy and angular distributions from the wedge slice images reveal a high momentum transfer during the ion-pair dissociation process, which could be the finest rationale to observe the breakdown of dipole Born approximation driven by multipole moment associated with the incident electron beam. Three distinct dissociative momentum bands have been precisely identified for O- dissociation. However, radiationless Rydberg's predissociation continuum (≥15%) has become an inherent character of electron-induced ion-pair dissociation, which could be dealt with using the beyond Born-Oppenheimer treatment. The incoherent sum of Σ and Π symmetric-associated ion-pair final states has been precisely identified by modeling the angular distribution of O-/O2 for each of the kinetic energy bands. A negligibly small amount of forward-backward asymmetry is observed in the angular distribution of O-/O2, which might be explained by the dissociative state-specific quantum coherence mechanism as reported [Krishnakumar et al., Nat. Phys. 14, 149 (2018); Kumar et al., arXiv:2206.15024 (2022)] by Prabhudesai et al.