Reaction Mechanism and Product Branching Ratios of OH+C2H3F Reaction:A Theoretical Study  

OH+C2H3F的反应机理及产物支化比反应的理论研究

作　　者：Chih-Hao Chin Tong Zhu John Zeng-Hui Zhang Chih-Hao Chin;Tong Zhu;John Zeng-Hui Zhang(华东师范大学化学与分子工程学院,上海200062;上海纽约大学计算化学联合中心,上海200062;美国纽约大学化学系,纽约10003)

机构地区：[1]School of Chemistry and Molecular Engineering,East China Normal University,Shanghai 200062,China [2]NYU-ECNU Center for Computational Chemistry at NYU Shanghai,Shanghai 200062,China [3]Department of Chemistry,New York University,New York 10003,United States of America

出　　处：《Chinese Journal of Chemical Physics》2020年第2期203-209,I0003,共8页化学物理学报（英文）

基　　金：supported by the National Natural Science Foundation of China (No.91641116).

摘　　要：Ab initio CCSD(T)/CBS//B3LYP/6-311G(d,p)calculations of the potential energy surface for possible dissociation channels of HOC2H3F,as well as Rice-Ramsperger-Kassel-Marcus(RRKM)calculations of rate constants,were carried out,in order to predict statistical product branching ratios in dissociation of HOC2H3F at various internal energies.The most favorable reaction pathway leading to the major CH2CHO+HF products is as the following:OH+C2H3F→i2→TS14→i6→TS9→i3→TS3→CH2CHO+HF,where the rate-determining step is HF elimination from the CO bridging position via TS11,lying above the reactants by 3.8 kcal/mol.The CH2O+CH2F products can be formed by F atom migration from Cαto Cβposition via TS14,then H migration from O to Cαposition via TS16,and C-C breaking to form the products via TS5,which is 1.8 kcal/mol lower in energy than the reactants,and 4.0 kcal/mol lower than TS11.

关 键 词：Ab initio Potential energy surface Reaction mechanism Rice-Ramsperger-Kassel-Marcus Branching ratio 

分 类 号：O643.12[理学—物理化学]