SUBPICOSECOND RESOLUTION STUDIES OF THE H-]CO+OH REACTION PHOTOINITIATED IN CO2-HI COMPLEXES(CO2)

Time resolved studies of the title reaction have been carried out by p hotodissociating the HI moiety within weakly bound CO2-HI complexes. T he HOCO(dagger) intermediate decomposes via a unimolecular decompositi on mechanism, and the emerging hydroxyl radicals are monitored with su bpicosecond temporal resolution by using laser-induced fluorescence. T he measured rates are in good agreement with several theoretical predi ctions: Rice, Ramsperger, Kassel, and Marcus (RRKM) calculations; clas sical trajectory simulations on the best available potential energy su rface; and recent quantum scattering calculations.