Dissociative Photodetachment Dynamics of the OH^-(C₂H₄) Anion Complex

Photoelectron-photofragment coincidence (PPC) measurements on OH^-(C₂H₄) anions at a photon energy of 3.20 eV revealed stable and dissociative photodetachment product channels, OH-C₂H₄ + e^- and OH + C₂H₄ + e^-, respectively. The main product channel observed was dissociation to the reactants (>67%), OH + C₂H₄ (v = 0, 1, 2) + e^-, where vibrational excitation in the C-H stretching modes of the C₂H₄ photofragments corresponds to a minor channel. The low kinetic energy release (KER) of the dissociating fragments is consistent with weak repulsion between the OH + C₂H₄ reactants near the transition state as well as the partitioning of energy into rotation of the dissociation products. An impulsive model was used to account for rotational energy partitioning in the dissociative photodetachment (DPD) process and showed good agreement with the experimental results. The low KER of the dissociating fragments and the similarities in the photoelectron spectra between stable and dissociative events support a mechanism involving the van der Waals complex formed upon photodetachment of OH^-(C₂H₄) as an intermediate in the dominant OH + C₂H₄ + e^- dissociative channel.