title: Ultraviolet Photodissociation Dynamics of the 1-Propenyl Radical.
abstract: Ultraviolet (UV) photodissociation dynamics of jet-cooled 1-propenyl radical (CHCHCH3) were investigated at the photolysis wavelengths from 224 to 248 nm using high-n Rydberg atom time-of-flight (HRTOF) technique. The 1-propenyl radicals were produced from 193 nm photolysis of 1-chloropropene and 1-bromopropene precursors. The photofragment yield (PFY) spectra of the H atom product have a broad peak centered at 230 nm. The H + C3H4 product translational energy P(ET) distribution's peak near ∼8 kcal/mol, and the fraction of average translational energy in the total available energy, ⟨fT⟩, is nearly a constant of ∼0.12 from 224 to 248 nm. The H atom product has an isotropic angular distribution with the anisotropy parameter β ≈ 0. Quasiclassical trajectory calculations were also carried out using an ab initio ground-state potential energy surface for dissociation of 1-propenyl at the excitation energy of 124 kcal/mol (230 nm). The calculated branching ratios are 60% to the methyl + acetylene products, 16% to H + propyne, 4% to H + allene, and 1% to H + cyclopropene. The experimental and calculated P(ET) distributions of the H + C3H4 products at 230 nm are in a qualitative agreement, suggesting that the H + propyne dissociation is the main H atom product channel. The calculated dissociation time scale on the ground electronic state is ∼1 ps, shorter than but close to the time scale of >10 ps for the overall UV photodissociation implied by the isotropic H atom product angular distribution. The UV photodissociation mechanism of 1-propenyl can be described as unimolecular decomposition of hot 1-propenyl radical on the ground electronic state following internal conversion from the electronically excited states of 1-propenyl.
authors.affiliation: Department of Chemistry, University of California at Riverside , Riverside, California 92521, United States.
authors.forename: Michael
authors.initials: M
authors.lastname: Lucas
authors.affiliation: Department of Chemistry, University of California at Riverside , Riverside, California 92521, United States.
authors.forename: Yu
authors.initials: Y
authors.lastname: Song
authors.affiliation: Department of Chemistry and Air Pollution Research Center, University of California at Riverside , Riverside, California 92521, United States.
authors.forename: Jingsong
authors.initials: J
authors.lastname: Zhang
authors.affiliation: Department of Chemistry and Biochemistry, California State University , Long Beach Long Beach, California 90840, United States.
authors.forename: Christopher
authors.initials: C
authors.lastname: Brazier
authors.affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology , Atlanta, Georgia 30332.|Department of Chemical Biology, Cornell University , Ithaca, New York 14850, United States.
authors.forename: Paul L
authors.initials: PL
authors.lastname: Houston
authors.affiliation: Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University , Atlanta, Georgia 30322, United States.
authors.forename: Joel M
authors.initials: JM
authors.lastname: Bowman