Theoretical Investigation of the NO3 Initiated Reaction of VOCs

Abstract

We have studied the reaction mechanism for the NO3 radical initiated atmospheric oxidation of three cresol isomers, p-cresol, m-cresol and o-cresol, in the presence of NO2. We have focused on the reaction mechanism leading to the ring retaining products, methyl-nitrophenol isomers and methyl-benzoquinone isomers. Geometries of the reactants, intermediates, transition states, and products have been optimized at the DFT-B3LYP level of theory with the 6-311 + G(d,p) basis set. The single point energy calculations have been carried out at the CCSD(T) level of theory with the cc-pVDZ basis set. The reaction path where the NO3 and NO2 radicals are added ipso and ortho to the OH group of the cresol isomer, respectively, has the lowest energy barrier. © Springer Science+Business Media Dordrecht 2013.