Quantum chemical study on the atmospheric photooxidation of methyl vinyl ether (MVE)

The reactions of methyl vinyl ether (MVE, CH3OCH=CH2) with OH radicals have been studied using density functional theory (DFT/B3LYP) with the 6-31G(*) basis set. The geometries and frequencies of all the stationary points and the minimum energy paths (MEPs) are calculated at the B3LYP/6-31G(*) level. The energetic information along the MEPs is further refined at the MP2/6-311 + G(**) level of theory. Three reaction pathways have been considered: one H abstraction and two OH additions to >C=C< bonds. A complete description of the possible degradation mechanisms in the presence Of 02 and NO, has been calculated and discussed. The detailed profiles of the potential energy surfaces (PESs) for the reactions are also explained. The calculations show that the most energetically favorable isomer is that of OH addition to the terminal carbon positions (C3 atom). The main products of the OH-initiated atmospheric photooxidation of MVE are methyl formate, formaldehyde and the glycolic acid methyl ester. (C) 2008 Elsevier B.V. All rights reserved.