Mechanistic studies of the reactions of nitrogen dioxide with dimethyl ether and methyl ethyl ether

Abstract

Ab initio and direct kinetics study of the CH3OCH3 + NO2 and CH3OC2H5 + NO2 reactions was performed over the temperature range of 300–1500 K. The geometries of all stationary points were optimized at the M06-2X/cc-pVTZ level of theory and the electronic energies were refined by the CCSD(T)/CBS method. The rate coefficients calculated by CVT theory including the small curvature tunneling (SCT) correction agreed well with the experimental data. Note that the H-abstraction from ethers to produce cis-HONO was the dominant channel at temperatures lower than 1000 K and the three channels to produce HNO2, trans-HONO and cis-HONO proceeded simultaneously.