Theoretical mechanistic study of OH-initiated atmospheric oxidation reaction of allyl alcohol in the presence of O2 and NO

The potential energy surfaces for the degradation mechanism of OH-initiated allyl alcohol oxidation in the atmosphere have been investigated in detail using QCISD(T)/6-311++G(d,p)//MP2(full)/6-311++G(d,p)+ZPE x 0.95 level of theory for the first time. The theoretical results indicate that the initial OH additions to the double bond will be more feasible than the H abstraction reactions. Two initial formed OH radical adducts IM1 and IM2 will prefer to react with O-2 and NO rather than undergo its self isomerization and dissociation reactions. Our calculational investigations suggest that the major products for the title reaction in the atmosphere are HCHO + CH2OHCHO, and the minor product is CH2=CHCHO, which all agree well with the available experimental results. (C) 2011 Elsevier B.V. All rights reserved.