Absolute Rate Coefficient and Mechanism of Gas Phase Reaction of Ketenyl Radical and SO2

作者：Du Lin^*; Carl Shaun A

来源：Journal of Physical Chemistry A, 2012, 116(41): 10074-10081.

DOI：10.1021/jp308457m

The kinetics of the gas phase reaction of the ketenyl radical with SO2 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 (CH2CO) 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) x 10(-12) exp[(690 +/- 98)K/T] cm(3) s(-1) molecule(-1) (2 sigma 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 SO2.

• 出版日期2012-10-18