The overlooked role of excited anion states in NiO₂⁻ photodetachment

Photodetachment spectra of anionic species provide significant insights into the energies and nature of ground and excited states of both the anion and resultant neutral molecules. Direct detachment of the excess electron to the continuum may occur via formally allowed or forbidden transitions (perhaps as the result of intensity borrowing through vibronic coupling). However, alternate indirect pathways are also possible and often overlooked. Here, we report a two-dimensional photoelectron spectral study, combined with correlated electronic structure calculations, to elucidate the nature of photodetachment from NiO₂⁻. The spectra are comprised of allowed and forbidden transitions, in excellent agreement with previously reported slow electron velocity mapped imaging spectra of the same system, which were interpreted in terms of direct detachment. In the current work, the contributions of indirect processes are revealed. Measured oscillations in the branching ratios of the spectral channels clearly indicate non-direct detachment processes, and the electronic structure calculations suggest that excited states of the appropriate symmetry and degeneracy lie slightly above the neutral ground state. Taken together, the results suggest that the origin of the observed forbidden transitions is the result of anion excited states mediating the electron detachment process.