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Reaction Mechanism and Product Branching Ratios of OH+C2H3F Reaction: A Theoretical Study
Chih-Hao Chin*1,2, Tong Zhu*1,2, John Zeng-Hui Zhang1,2,3
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
Abstract:
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 Cα to Cβ position via TS14, then H migration from O to Cα position 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.
Key words:  Ab initio, Potential energy surface, Reaction mechanism, Rice-Ramsperger-Kassel-Marcus, Branching ratio
FundProject:
Supplymentary:   CJCP2001016SP.pdf
OH+C2H3F的反应机理及产物支化比反应的理论研究
Chih-Hao Chin*1,2, Tong Zhu*1,2, John Zeng-Hui Zhang1,2,3
1.华东师范大学化学与分子工程学院,上海 200062;2.上海纽约大学计算化学联合中心,上海 200062;3.美国纽约大学化学系,纽约 10003
摘要:
本文对HOC2H3F可能解离通道的势能面进行从头算CCSD(T)/CBS//B3LYP/6-311G(d,p)计算,同时对速率常数进行Rice-Ramsperger-Kassel-Marcus计算. 生成主要产物CH2CHO+HF最有利的反应途径是OHC2H3F→i2→TS14→i6→TS9→i3→TS3→CH2CHO+HF,其中速率决定步骤是HF通过TS11从CO桥接位置解离,能量比反应物高3.8 kcal/mol. 借助中间态TS14,F原子从Cα迁移到Cβ位置生成CH2O+CH2F,然后通过中间态TS16,H从O迁移到Cα位置;通过中间态TS5,C-C键断裂生成产物,其能量比反应物低1.8 kcal/mol,比TS11低4.0 kcal/mol.
关键词:  从头算,势能面,反应机理,Rice-Ramsperger-Kassel-Marcus,产物分支比
DOI:10.1063/1674-0068/cjcp2001016
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