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.