Theoretical Study on the Reaction of (Z)-CF_3CH=CHCF_3 with OH Radicals

摘要

The mechanism on the OH-initiated atmospheric oxidation reaction of (Z)-CF_3CH=CHCF_3 with and without O_2/NO has been investigated theoretically. The electronic structure information of the potential energy surface was obtained at the M06-2X/aug-cc-pVDZ level, and the single-point energies were refined by MCG3/3 method. The calculations show that the (Z)-CF_3CH=CHCF_3 + OH reaction occurs via additionelimination mechanism, leading to products CF_3 and CF_3CH=CH(OH), rather than H-abstraction mechanism at low temperature. Under atmospheric condition, the OH-addition intermediate is likely to react rapidly with O_2/NO, and the likely products are CF_3C(O)H, CF_2(O), CF_3CH(OH)CH(O), FNO, and HO_2, as is proposed by experiment.