O₂^-·[Polar VOC] Complexes: H-Bonding versus Charge-Dipole Interactions, and the Noninnocence of Formaldehyde

Anion photoelectron imaging was used to measure the photodetachment spectra of molecular complexes formed between O₂^- and a range of atmospherically relevant polar molecules, including species with a carbonyl group (acetone, formaldehyde) and alcohols (ethanol, propenol, butenol). Experimental spectra are analyzed using a combination of Franck-Condon simulations and electronic structure calculations. Strong charge-dipole interactions and H-bonding stabilize the complex anions relative to the neutrals, resulting in a ca. 1 eV increase in electron binding energy relative to bare O₂^-, an effect more pronounced in complexes with H-bonding. In addition, broken degeneracy of the O₂-local π_g orbitals in the complexes results in the stabilization of the low-lying excited O₂ (a ¹Δ_g)·[polar VOC] state relative to the ground O₂ (X ³Σ_g^-)·[polar VOC] state when compared to bare O₂. The spectra of the O₂^-·[polar VOC] complexes exhibit less pronounced laser photoelectron angular distribution (PADs). The spectrum of O₂^-·formaldehyde is unique in terms of both spectral profile and PAD. On the basis of these experimental results in addition to computational results, the complex anion cannot be described as a distinct O₂^- anion partnered with an innocent solvent molecule; the molecules are more strongly coupled through charge delocalization. Overall, the results underscore how the symmetry of the O₂ π_g orbitals is broken by different polar partners, which may have implications for atmospheric photochemistry and models of solar radiation absorption that include collision-induced absorption.