A dynamic method is employed to study the reaction mechanisms of CH3CH2OCF3 with the hydrogen trioxy （HOOO） radical. In our paper, the geometries and harmonic vibrational frequencies of all the stationary points and...A dynamic method is employed to study the reaction mechanisms of CH3CH2OCF3 with the hydrogen trioxy （HOOO） radical. In our paper, the geometries and harmonic vibrational frequencies of all the stationary points and minimum energy paths （MEPs） are calculated at the MPW1K/6-31＋G（d,p） level of theory, and the energetic information along MEPs is further refined by the CCSD/6-31＋G（df, p） level of theory. The rate constants are evaluated with the conventional transition-state theory （TST）, the canonical variational transition-state theory （CVT）, the microcanonical variational transition-state theory （μVT）, the CVT coupled with the small-curvature tunneling （SCT） correction （CVT/SCT）, and the μVT coupled with the Eckart tunneling correction μVT/Eckart） based on the ab initio calculations in the temperature range of 200-3000 K. The theoretical results are important in determining the atmospheric lifetime and the feasible pathways for the loss of HFEs.展开更多
基金supported by the the National Natural Science Foundation of China(No.21373025 and 20933001)the Research Foundation of Education Bureau of Hebei Province(No.Z2011115)+3 种基金the 111 Project of China(No.B07012)the Natural Science Foundation of Hebei Province(No.B2012105002)the Research Foundation of Tangshan Administration of Science&Technology(131302115b)the Research Foundation of Tangshan normal college(2013A04)
文摘A dynamic method is employed to study the reaction mechanisms of CH3CH2OCF3 with the hydrogen trioxy （HOOO） radical. In our paper, the geometries and harmonic vibrational frequencies of all the stationary points and minimum energy paths （MEPs） are calculated at the MPW1K/6-31＋G（d,p） level of theory, and the energetic information along MEPs is further refined by the CCSD/6-31＋G（df, p） level of theory. The rate constants are evaluated with the conventional transition-state theory （TST）, the canonical variational transition-state theory （CVT）, the microcanonical variational transition-state theory （μVT）, the CVT coupled with the small-curvature tunneling （SCT） correction （CVT/SCT）, and the μVT coupled with the Eckart tunneling correction μVT/Eckart） based on the ab initio calculations in the temperature range of 200-3000 K. The theoretical results are important in determining the atmospheric lifetime and the feasible pathways for the loss of HFEs.
