Dissociative photodetachment of internally cold HOCO¯ has been performed in a new cryogenically cooled photoelectron−photofragment coincidence apparatus, characterizing the HOCO potential energy surface in the Franck−Condon region determined by the anion. Three processes are observed in three distinct regions of this surface: detachment to stable HOCO, dissociative photodetachment to OH + CO, and dissociative photodetachment to H + CO 2 . Relative to earlier work on internally hot anions, the H + CO 2 channel is significantly enhanced, with efficient dissociation to H + CO 2 unambiguously detected below calculated barriers in the OH + CO → H + CO 2 reaction. This finding shows that an important low-energy pathway exists to the exit channel in this reaction, reinforcing the need for further refinement of this important potential energy surface and providing benchmarks for further theoretical efforts.
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Johnson et al. (2010) studied this question.