title: Absolute rate coefficient and mechanism of gas phase reaction of ketenyl radical and SO2.
abstract: The kinetics of the gas phase reaction of the ketenyl radical with SO(2) was investigated over the temperature range 296-568 K using a laser-photofragment/laser-induced fluorescence technique (LP/LIF). The reactor pressure was 10 Torr N(2) or He. Pulsed photolysis of ketene (CH(2)CO) at 193 nm was used as the source of HCCO radicals. The rate coefficient for the title reaction was determined to be described by k(T) = (1.05 ± 0.33) × 10(-12) exp[(690 ± 98)K/T] cm(3) s(-1) molecule(-1) (2σ error). We applied the coupled cluster and density functional theory to explore the mechanism of the title reaction. The dominant reaction pathway begins with a barrierless association of the C of the CH group of HCCO and the O atom of SO(2).
authors.affiliation: Department of Chemistry, Katholieke Universiteit Leuven, B-3001 Leuven, Belgium. lindu@chem.ku.dk
authors.forename: Lin
authors.initials: L
authors.lastname: Du
authors.forename: Shaun A
authors.initials: SA
authors.lastname: Carl
mesh_terms: D005030:Ethylenes / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D007700:Kinetics; D007834:Lasers; D011789:Quantum Theory; D013458:Sulfur Dioxide / Q000737:chemistry*; D013696:Temperature
chemical_list: D005030:Ethylenes; D005609:Free Radicals; D007659:Ketones; D013458:Sulfur Dioxide; C008223:ketene