Photoelectron spectroscopy of cryogenically cooled NiO₂⁻via slow photoelectron velocity-map imaging

High-resolution anion photoelectron spectra of cryogenically cooled NiO₂⁻ anions, obtained using slow photoelectron velocity-map imaging (cryo-SEVI), are presented in tandem with coupled cluster electronic structure calculations including relativistic effects. The experimental spectra encompass the X̃¹Σ_g⁺ ← X̃²Π_g, ã³Π_g ← X̃²Π_g, and ùΠ_g ← X̃²Π_g photodetachment transitions of linear ONiO^0/−, revealing previously unobserved vibrational structure in all three electronic bands. The high-resolution afforded by cryo-SEVI allows for the extraction of vibrational frequencies for each state, consistent with those previously measured in the ground state and in good agreement with scalar-relativistic coupled-cluster calculations. Previously unobserved vibrational structure is observed in the ã³Π_g and ùΠ_g states and is tentatively assigned. Further, a refined electron affinity of 3.0464(7) eV for NiO₂ is obtained as well as precise term energies for the ã and à states of NiO₂ of 0.3982(7) and 0.7422(10) eV, respectively. Numerous Franck-Condon forbidden transitions involving the doubly degenerate ν₂ bending mode are observed and ascribed to Herzberg-Teller coupling to an excited electronic state.