Theoretical investigation of an atmospherically important reaction between methyl methacrylate and Cl atom: A mechanistic and kinetic approach

Abstract

A theoretical investigation of the mechanism, kinetics and probable product analysis of the Cl -initiated oxidation reaction of methyl methacrylate (MMA) is presented in this paper. The major degradation pathway of MMA is the Cl -addition to the terminal carbon of the olefinic bond. Beside this, energetic and mechanism of other possible reaction pathways are discussed in detail. In addition, the mechanism for the secondary reactions in presence of O 2 and NO has also been presented. Cl -addition to the double bond takes place via formation of the pre-reactive complex as these reaction channel passes through negative activation barrier. Energetics and thermochemical analysis have been studied at the MP2=Full/6-311++g(d,p) level of theory. The rate constant of the Cl -addition reaction has been calculated using conventional transition state theory (CTST) at 1 atm pressure and 250–350 K temperature range.