Theoretical study on mechanism, kinetics, and thermochemistry of the gas phase reaction of 2,2,2-trifluoroethyl butyrate with OH radicals at 298 K

Abstract

A theoretical investigation has been carried out on the mechanism, kinetics, and thermochemistry of gas-phase reaction of 2,2,2-trifluoroethyl butyrate (TFEB, CH3CH2CH2C(O)OCH2CF3) with OH radicals using a modern DFT functional. The involvement of pre- and post-reactive complexes was explored and the reaction profiles were modeled. Energetic calculations were performed using the M06-2X/6-31 + G(d,p) method. The intrinsic reaction coordinate (IRC) calculation has been performed to confirm the smooth transition from the reactant to product through the respective transition state. It has been found that the dominant path of the H-atom abstraction takes place from the –CH2- position, which is attached with the methyl group at the one end of TFEB. Theoretically calculated rate constant at 298 K using canonical transition state theory (CTST) is found to be in reasonable agreement with the experimental data. Using group-balanced isodesmic procedure, the standard enthalpy of formation for TFEB is reported for the first time. The branching ratios of the different reaction channels are also determined. The atmospheric lifetime of TFEB is determined to be 6.8 days. The reaction kinetics of H-atom abstraction reaction of 2,2,2-trifluoroethyl butyrate (TFEB) with OH radicals was investigated at M06-2X/6-31+G (d,p) level of theory. The branching ratios of the different reaction channels are also determined. The atmospheric lifetime of TFEB is estimated to be 6.8 days.