The anion photoelectron imaging spectra of O·VOC and O·VOC (VOC = hexane, isoprene, benzene, and benzene-d) complexes measured using 3.49 eV photon energy, along with the results of ab initio and density functional theory results are reported and analyzed. Photodetachment of these anionic complexes accesses neutrals that model collision complexes, offering a probe of the effects of symmetry-breaking collision events on the electronic structure of normally transparent neutral molecules. The energies of O·VOC spectral features compared to the bare O indicate that photodetachment of the anion accesses a modestly repulsive region of the O-VOC potential energy surface, with subtle VOC dependence on the relative energies of the O (X Σ)·VOC ground state and O (a Δ)·VOC excited state. In contrast, a significantly higher intensity of the transition to the O (a Δ)·VOC excited state relative to the O (X Σ)·VOC ground state is observed for VOC = benzene, with a less pronounced effect observed for VOC = isoprene. Similar spectral effects are observed in the O·benzene and O·isoprene PE spectra. Several explanations are considered, with involvement of a temporary anion state emerging as the most plausible.

Anion photoelectron imaging was used to measure the photodetachment spectra of molecular complexes formed between O 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 O, an effect more pronounced in complexes with H-bonding. In addition, broken degeneracy of the O-local π orbitals in the complexes results in the stabilization of the low-lying excited O (a Δ)·[polar VOC] state relative to the ground O (X Σ)·[polar VOC] state when compared to bare O. The spectra of the O·[polar VOC] complexes exhibit less pronounced laser photoelectron angular distribution (PADs). The spectrum of O·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 O 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 O π 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.

The anion photoelectron imaging spectra of an ion with m/z 85, generated under ion source conditions that optimize •OH production in a coexpansion with isoprene, are presented and analyzed with supporting calculations. A spectroscopic feature observed at a vertical electron detachment energy of 2.45 eV, which dominates the photoelectron spectrum measured at 3.495 eV photon energy, is consistent with the OH–·isoprene ion–molecule complex, while additional signal observed at lower electron binding energy can be attributed to other constitutional isomers. However, spectra measured over a 2.2–2.6 eV photon energy range, i.e., from near threshold of the predominant OH–·isoprene detachment feature through the vertical detachment energy, exhibit sharp features with common electron kinetic energies, suggesting autodetachment from a temporary anion prepared by photoexcitation. The photon energy independence of the electron kinetic energy of these features along with the low dipole moment predicted for the neutral •OH·isoprene van der Waals complex, suggest a complex photon-driven process. We present calculations supporting a hypothesis that near-threshold production of the •OH···isoprene reactive complex results in hydrogen abstraction of the isoprene molecule. The newly formed activated complex anion supports a dipole bound state that temporarily traps the near zero-kinetic energy electron and then autodetaches, encoding the low-frequency modes of the dehydrogenated neutral isoprene radical in the electron kinetic energies.

Photoelectron imaging spectra of three alkenoxide radical anions (3-buten-1-oxide, 3-buten-2-oxide, and 2-propenoxide) are presented and analyzed with supporting results of density functional theory calculations. In all spectra, intense detachment features are observed at approximately 2 eV electron binding energy, which is similar to the electron affinities of saturated neutral alkoxy radicals [Ramond et al., J. Chem. Phys. 112, 1158]. Photoelectron angular distributions suggest the presence of several overlapping transitions which are assigned to theX andà states of multiple energetically competitive conformers. The term energy of theà state of the 2-propenoxy radical, 0.17 eV, is higher than that of 3-buten-2-oxy (0.13 eV) and 3-buten-1-oxy (0.05 eV) radicals. Comparing the butenoxy radicals, we infer that stronger interactions between the non-bonding O 2p orbitals and the π bond increase the splitting between the ground and the first excited state in the 3-buten-2-oxy radical relative to the 3-buten-1-oxy radical.

Perturbations of the bare O2-and O4-electronic structure arising from VOC (VOC = hexane, isoprene, benzene and benzene.D6) interactions are investigated using anion photoelectron imaging at 2.33 and 3.49 eV photon energies. Trends observed from comparing features in the spectra include VOC-identity-dependent electron affinities of the VOC complexes relative to the bare oxide clusters, due to enhance stability in the anion complex relative to the neutral. Autodetachment is observed in all O4-.VOC spectra and only isoprene with O2-. In addition, the intensities of transitions to states correlated with the singlet states of O2 neutral via detachment from the O2-.VOC anion complexes show dramatic VOC-identity variations. Most notably, benzene as a complex partner significantly enhances these transitions relative to O2-and O2-.hexane. A less significant enhancement is also observed in the O2-.isoprene complex. This enhancement may be due to the presence of low-lying triplet states in the complex partners.