The dynamics of CO production from the photolysis of acetone across the whole S1 ← S0 absorption spectrum: Roaming and triple fragmentation pathways

The unimolecular photodissociation dynamics of acetone spanning the entire S1 ← S0 absorption spectrum have been reinvestigated, with a focus on mechanisms that produce CO. At excitation wavelengths of λ > 305.8 nm, all photoproducts are formed on the S0 state after internal conversion. A roaming mechanism forming C2H6 + CO is active in the window λ = 311.2–305.8 nm. From λ = 305.8 to 262 nm, little or no CO is produced with the photochemistry dominated by the Norrish-type I C–C bond cleavage on the lowest excited triplet state, T1. At higher energy ( λ < 262 nm), an increasing fraction of CH3CO radicals from the primary reaction have sufficient internal energy to spontaneously decompose to CH3 + CO. A new model is presented to account for the kinetic energy distribution of the secondary CH3 radical, allowing us to determine the height of the energetic barrier to CH3CO decomposition as 68 ± 4 kJ mol−1, which lies midway between previous measurements. The fraction of CO from triple fragmentation rises smoothly from 260 to 248 nm. We see no evidence of the return of roaming, or any other S0 reaction, in this higher energy region of the first electronic absorption band.