Autodetachment over Broad Photon Energy Ranges in the Anion Photoelectron Spectra of [O2– M ]− ( M = Glyoxal, Methylglyoxal, or Biacetyl) Complex Anions

Complexes of anion–neutral pairs are prevalent in chemical and physical processes in the interstellar medium, the atmosphere, and biological systems, among others. However, bimolecular anionic species that cannot be described as simple ion–molecule complexes due to their competitive electron affinities have received less attention. In this study, the [O2– M ]− ( M = glyoxal, methylglyoxal, or biacetyl) anion photoelectron spectra obtained with several different photon energies are reported and interpreted in the context of ab initio calculations. The spectra do not resemble the photoelectron spectra of M – or O2 – “solvated” by a neutral partner. Rather, all spectra are dominated by near-threshold autodetachment from what are likely transient dipole bound states of the cis conformers of the complex anions. Very low Franck–Condon overlap between the neutral M ·O2 van der Waals clusters and the partial covalently bound complex anions results in low-intensity, broad direct detachment observed in the spectra. The [O2-glyoxal]− spectra measured with 2.88 and 3.495 eV photon energies additionally exhibit features at ∼0.5 eV electron kinetic energy, which is more difficult to explain, though there are numerous quasibound states of the anion that may be involved. Overall, these features point to the inadequacy of describing the complex anions as simple ion–molecule complexes.