title: Oxidation of the para-Tolyl Radical by Molecular Oxygen under Single-Collison Conditions: Formation of the para-Toloxy Radical.
abstract: Crossed molecular beam experiments were performed to elucidate the chemical dynamics of the para-tolyl (CH3C6H4) radical reaction with molecular oxygen (O2) at an average collision energy of 35.3 ± 1.4 kJ mol-1. Combined with theoretical calculations, the results show that para-tolyl is efficiently oxidized by molecular oxygen to para-toloxy (CH3C6H4O) plus ground-state atomic oxygen via a complex forming, overall exoergic reaction (experimental, -33 ± 16 kJ mol-1; computational, -42 ± 8 kJ mol-1). The reaction dynamics are analogous to those observed for the phenyl (C6H5) plus molecular oxygen system which suggests the methyl group is a spectator during para-tolyl oxidation and that application of phenyl thermochemistry and reaction rates to para-substituted aryls is likely a suitable approximation.
authors.affiliation: Department of Chemistry, University of Hawai'i at Ma̅noa , Honolulu, Hawaii 96822, United States.
authors.forename: Aaron M
authors.initials: AM
authors.lastname: Thomas
authors.affiliation: Department of Chemistry, University of Hawai'i at Ma̅noa , Honolulu, Hawaii 96822, United States.
authors.forename: Tao
authors.initials: T
authors.lastname: Yang
authors.affiliation: Department of Chemistry, University of Hawai'i at Ma̅noa , Honolulu, Hawaii 96822, United States.
authors.forename: Beni B
authors.initials: BB
authors.lastname: Dangi
authors.affiliation: Department of Chemistry, University of Hawai'i at Ma̅noa , Honolulu, Hawaii 96822, United States.
authors.forename: Ralf I
authors.identifier: http://orcid.org/0000-0002-7233-7206
authors.initials: RI
authors.lastname: Kaiser
authors.affiliation: Dharma College, Dongguk University , 30, Pildong-ro 1-gil, Jung-gu, Seoul 04620, South Korea.
authors.forename: Gap-Sue
authors.initials: GS
authors.lastname: Kim
authors.affiliation: Department of Chemistry and Biochemistry, Florida International University , Miami, Florida 33199, United States.
authors.forename: Alexander M
authors.identifier: http://orcid.org/0000-0002-7233-3133
authors.initials: AM
authors.lastname: Mebel