Dynamics on the HOCO potential energy surface studied by dissociative photodetachment of HOCO- and DOCO-.

An experimental study of the dissociative photodetachment (DPD) dynamics of HOCO(-) and DOCO(-) at a photon energy of 3.21 eV has been carried out to probe the potential energy surface of the HOCO free radical and the dynamics of the OH+CO-->H+CO(2) reaction. These photoelectron-photofragment coincidence experiments allow the identification of photodetachment processes leading to the production of stable HOCO free radicals and both the H+CO(2) and OH+CO dissociation channels on the neutral surface. Isotopic substitution by deuterium in the parent ion is observed to reduce the product branching ratio for the D+CO(2) channel, consistent with tunneling playing a role in this dissociation pathway. Other isotope effects on the detailed partitioning of kinetic energy between photoelectrons and photofragments are also discussed. The results are compared to recent theoretical predictions of this DPD process, and evidence for the involvement of vibrationally excited HOCO(-) anions is discussed.