Reaction dynamics of phenyl radicals in extreme environments: a crossed molecular beam study.
Polycyclic aromatic hydrocarbons (PAHs)organic compounds that consist of fused benzene ringsand their hydrogen-deficient precursors have attracted extensive interest from combustion scientists, organic chemists, astronomers, and planetary scientists. On Earth, PAHs are toxic combustion products and a source of air pollution. In the interstellar medium, research suggests that PAHs play a role in unidentified infrared emission bands, diffuse interstellar bands, and the synthesis of precursor molecules to life. To build clean combustion devices and to understand the astrochemical evolution of the interstellar medium, it will be critical to understand the elementary reaction mechanisms under single collision conditions by which these molecules form in the gas phase. Until recently, this work had been hampered by the difficulty in preparing a large concentration of phenyl radicals, but the phenyl radical represents one of the most important radical species to trigger PAH formation in high-temperature environments. However, we have developed a method for producing these radical species and have undertaken a systematic experimental investigation. In this Account, we report on the chemical dynamics of the phenyl radical (C(6)H(5)) reactions with the unsaturated hydrocarbons acetylene (C(2)H(2)), ethylene (C(2)H(4)), methylacetylene (CH(3)CCH), allene (H(2)CCCH(2)), propylene (CH(3)CHCH(2)), and benzene (C(6)H(6)) utilizing the crossed molecular beams approach. For nonsymmetric reactants such as methylacetylene and propylene, steric effects and the larger cones of acceptance drive the addition of the phenyl radical to the nonsubstituted carbon atom of the hydrocarbon reactant. Reaction intermediates decomposed via atomic hydrogen loss pathways. In the phenyl-propylene system, the longer lifetime of the reaction intermediate yielded a more efficient energy randomization compared with the phenyl-methylacetylene system. Therefore, two reaction channels were open: hydrogen losses from the vinyl and from the methyl groups. All fragmentation pathways involved tight exit transition states. In the range of collision energies investigated, the reactions are dictated by phenyl radical addition-hydrogen atom elimination pathways. We did not observe ring closure processes with the benzene ring. Our investigations present an important step toward a systematic investigation of phenyl radical reactions under single collision conditions similar to those found in combustion flames and in high-temperature interstellar environments. Future experiments at lower collision energies may enhance the lifetimes of the reaction intermediates, which could open up competing ring closure channels to form bicyclic reaction products.
Gu
Xibin
X
Department of Chemistry, University of Hawaii at Manoa, Honolulu, Hawaii 96822, USA.
Kaiser
Ralf I
RI
D000818:Animals; D002627:Chemistry, Physical / Q000295:instrumentation / Q000379:methods; D005118:Extraterrestrial Environment; D005609:Free Radicals / Q000737:chemistry*; D005740:Gases / Q000737:chemistry; D006801:Humans; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D013816:Thermodynamics
D005609:Free Radicals; D005740:Gases; D011084:Polycyclic Aromatic Hydrocarbons