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Atomic oxygen in its first excited singlet state, O(1 D), is an importantspecies in the photochemistry of several planetary atmospheres and has beenpredicted to be a potentially important reactive species on interstellar ices.Here, we report the results of a kinetic study of the reactions of O(1 D) withmethanol, CH3OH, and acetonitrile, CH3CN, over the 50-296 K temperature range.A continuous supersonic flow reactor was used to attain these low temperaturescoupled with pulsed laser photolysis and pulsed laser induced fluorescence togenerate and monitor O(1 D) atoms respectively. Secondary experiments examiningthe atomic hydrogen product channels of these reactions were also performed,through laser induced fluorescence measurements of H(2 S) atom formation. Onthe kinetics side, the rate constants for these reactions were seen to be large(> 2 x 10-10 cm 3 s-1) and consistent with barrierless reactions, although theydisplay contrasting dependences as a function of temperature. On the productformation side, both reactions are seen to yield non-negligible quantities ofatomic hydrogen. For the O(1 D) + CH3OH reaction, the derived yields are ingood agreement with the conclusions of previous experimental and theoreticalwork. For the O(1 D) + CH3CN reaction, whose H-atom formation channels had notpreviously been investigated, electronic structure calculations of several newproduct formation channels were performed to explain the observed H-atomyields. These calculations demonstrate the barrierless and exothermic nature ofthe relevant exit channels, confirming that atomic hydrogen is also animportant product of the O(1 D) + CH3CN reaction.

A Kinetic Study of the Gas-Phase O( 1 D) + CH3OH and O( 1 D) + CH3CN Reactions. Low Temperature Rate Constants and Atomic Hydrogen Product Yields