Subpicosecond resolution studies of the H+CO2→CO+OH reaction photoinitiated in CO2–HI complexes

Abstract

Time resolved studies of the title reaction have been carried out by photodissociating the HI moiety within weakly bound CO2–HI complexes. The HOCO° intermediate decomposes via a unimolecular decomposition mechanism, and the emerging hydroxyl radicals are monitored with subpicosecond temporal resolution by using laser-induced fluorescence. The measured rates are in good agreement with several theoretical predictions: Rice, Ramsperger, Kassel, and Marcus (RRKM calculations; classical trajectory simulations on the best available potential energy surface; and recent quantum scattering calculations.