UC Irvine

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*.