Ab initio investigations of the radical-radical reaction of O(P3)+C3H3

Abstract

We present ab initio calculations of the reaction of ground-state atomic oxygen [O(P3)] with a propargyl (C3H3) radical based on the application of the density-functional method and the complete basis-set model. It has been predicted that the barrierless addition of O(P3) to C3H3 on the lowest doublet potential-energy surface produces several energy-rich intermediates, which undergo subsequent isomerization and decomposition steps to generate various exothermic reaction products: C2H3+CO, C3H2O+H, C3H2+OH, C2H2+CHO, C2H2O+CH, C2HO+CH2, and CH2O+C2H. The respective reaction pathways are examined extensively with the aid of statistical Rice-Ramsperger-Kassel-Marcus calculations, suggesting that the primary reaction channel is the formation of propynal (CHCCHO)+H. For the minor C3H2+OH channel, which has been reported in recent gas-phase crossed-beam experiments [H. Lee et al., J. Chem. Phys. 119, 9337 (2003); 120, 2215 (2004)], a comparison on the basis of prior statistical calculations is made with the nascent rotational state distributions of the OH products to elucidate the mechanistic and dynamic characteristics at the molecular level.