Acetylacetone Photolysis at 280 nm Studied by Velocity-Map Ion Imaging

The photolysis of acetylacetone (AcAc) has been studied using velocity-map ion imaging with pulsed nanosecond lasers. The enolone tautomer of AcAc (CH₃C(O)CH═C(OH)CH₃) was excited in the strong UV absorption band by UV pulses at 280 nm, preparing the S₂(ππ*) state, and products were probed after a short time delay by single-photon VUV ionization at 118.2 nm. Two-color UV + VUV time-of-flight mass spectra show enhancement of fragments at m/z = 15, 42, 43, 58, and 85 at the lowest UV pulse energies and depletion of the parent ion at m/z = 100. Ion images of the five major fragments are all isotropic, indicating dissociation lifetimes that are long on the timescale of molecular rotation but shorter than the laser pulse duration (<6 ns). The m/z = 15 and 85 fragments have identical momentum distributions with moderate translational energy release, suggesting that they are formed as a neutral product pair and likely via a Norrish type I dissociation of the enolone to form CH₃ + C(O)CH═C(OH)CH₃ over a barrier on a triplet surface. The m/z = 43 fragment may be tentatively assigned to the alternative Norrish type I pathway that produces CH₃CO + CH₂C(O)CH₃ on S₀ following phototautomerization to the diketone, although alternative mechanisms involving dissociative ionization of a larger primary photoproduct cannot be conclusively ruled out. The m/z = 42 and 58 fragments are not momentum-matched and consequently are not formed as a neutral pair via a unimolecular dissociation pathway on S₀. They also likely originate from the dissociative ionization of primary photofragments. RRKM calculations suggest that unimolecular dissociation pathways that lead to molecular products on S₀ are generally slow, implying an upper-limit lifetime of <46 ns after excitation at 280 nm. Time-dependent measurements suggest that the observed photofragments likely do not arise from dissociative ionization of energized AcAc S₀*.