Theoretical study on dynamics of the gas phase reactions of CF3CF2CH2OCHF2 with OH radicals

•Kinetics of the gas phase reaction of CF3CF2CH2OCHF2 + OH was investigated.•The reactivity of displacement and H-abstraction reaction is compared.•The rate constants of the H-abstraction pathways are calculated.

A theoretical study on the mechanism and dynamics properties of the gas-phase reaction of CF3CF2CH2OCHF2 + OH is performed by using BMK method with the 6-311+G(d,p) basis set. The energy is further refined by the BMC-CCSD theory on the basis of the optimized structures. There are two kinds of H-abstraction channels and two displacement channels. The reactivity of displacement and H-abstraction reaction is compared from both the thermodynamic and kinetic viewpoints. The contributions from displacement channels are negligible. For both H-abstraction channels, the H-abstraction from CH2 site is more favorable than that from CHF2 site. The rate constants of title reaction are firstly determined by theoretical method in a wide temperature range.

Graphical abstractBy using dual-level direct dynamics method (X//Y), schematic pathways and rate constants for the reaction CF3CF2CH2OCHF2 + OH are obtained. The predominant reaction pathway is hydrogen abstraction rather than displacement process.Figure optionsDownload full-size imageDownload as PowerPoint slide