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.

Identification of Isoprene Oxidation Reaction Products via Anion Photoelectron Spectroscopy.

We present a study on the oxidation of isoprene under several different conditions that may model both atmospheric and combustion chemistry. Anions, formed by passing isoprene/oxidant gas mixtures through a pulsed discharge generating a range of species, are separated via mass spectrometry and characterized by anion photoelectron (PE) spectroscopy supported by computations. Specifically, a UV-irradiated isoprene/O2 mixture, which additionally produces O3, and an isoprene/O2/H2 mixture, which generates •OH when passed through the discharge, were sampled. The mass spectra of ions generated under both conditions show the production of intact molecular ions, ion-molecule complexes (e.g., O2-, O4-, and O2-·isoprene), and singly deprotonated species (e.g., deprotonated isoprene, C5H7-). In addition, both smaller and oxidized fragments are observed using both gas mixtures, though relative abundances differ. From the UV-irradiated isoprene/O2 gas mixture, additional intact molecular products of reactions initiated by ozonolysis of isoprene, methylglyoxal, and dimethylglyoxal were observed. Fragmentation and oxidation of isoprene observed in both gas mixtures included species with m/z 39, 53, 67, 69, and 83 that we attribute to a series of alkyl- and alkenoxide-based anions. The coexistence of intact molecules and complexes with fragments and reaction products demonstrates the versatility of this ion source as a simple and efficient anion formation method for studying species that may be relevant in atmospheric and combustion chemistry.

Emerging Nonvalence Anion States of [Isoprene-H·]·H2O Accessed via Detachment of OH-·Isoprene.

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.

Temporary anion states of fluorine substituted benzenes probed by charge transfer in O2 -·C6H6-xFx (x = 0-5) ion-molecule complexes.

The broadband photoelectron source realized by detaching O2 -·X (X = neutral unsaturated molecule) complexes offers a unique opportunity to probe temporary anion states of the unsaturated species. Detachment of the ion molecule complex typically accesses a dissociative portion of the neutral potential, creating a continuum electron source that can undergo scattering with X. We present the application of this new approach to electron-neutral scattering toward a study of the series of fluorinated benzenes via photoelectron spectroscopy of O2 -·C6H6-xFx (x = 0-6) measured with several photon energies. We compare these spectra to the reference O2 -·hexane spectrum and observe evidence of temporary anion states of C6H6-xFx for species with x = 0-5 in the form of enhanced signal intensity at electron kinetic energies coinciding with the energies of the temporary anions. Furthermore, we observe autodetachment features in the x = 3, 5 spectra. Results of calculations on the isolated symmetric isomer of C6H3F3 suggest that the molecule cannot support a weakly-bound non-valence state that could be associated with the observed autodetachment. However, C6HF5 - is predicted to support a valence bound state, which, if produced by charge transfer from O2 - with sufficient vibrational energy, may undergo autodetachment. Finally, the [O2·C6F6]- spectrum is unique insofar as the spectrum is substantially higher in binding energy and qualitatively different from the x = 0-5 spectra. This result suggests much stronger interactions and charge delocalization between O2 - and C6F6.

Probing alkenoxy radical electronic structure using anion PEI spectroscopy.

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 (2000)]. Photoelectron angular distributions suggest the presence of several overlapping transitions which are assigned to the X̃ and à states of multiple energetically competitive conformers. The term energy of the à 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.