Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Renmin Road 5268., Changchun, Jilin 130024, P.R. China.
J Phys Chem A. 2012 Mar 29;116(12):3172-81. doi: 10.1021/jp209960c. Epub 2012 Mar 12.
The potential energy surfaces of the CF(3)CH═CH(2) + OH reaction have been investigated at the BMC-CCSD level based on the geometric parameters optimized at the MP2/6-311++G(d,p) level. Various possible H (or F)-abstraction and addition/elimination pathways are considered. Temperature- and pressure-dependent rate constants have been determined using Rice-Ramsperger-Kassel-Marcus theory with tunneling correction. It is shown that IM1 (CF(3)CHCH(2)OH) and IM2 (CF(3)CHOHCH(2)) formed by collisional stabilization are major products at 100 Torr pressure of Ar and in the temperature range of T < 700 K (at P = 700 Torr with N(2) as bath gas, T ≤ 900 K), whereas CH(2)═CHOH and CF(3) produced by the addition/elimination pathway are the dominant end products at 700-2000 K. The production of CF(3)CHCH and CF(3)CCH(2) produced by hydrogen abstractions become important at T ≥ 2000 K. The calculated results are in good agreement with available experimental data. The present theoretical study is helpful for the understanding the characteristics of the reaction of CF(3)CH═CH(2) + OH.
基于 MP2/6-311++G(d,p) 水平优化的几何参数，在 BMC-CCSD 水平上研究了 CF(3)CH═CH(2) + OH 反应的势能面。考虑了各种可能的 H（或 F）-消除和加成/消除途径。使用包含隧道效应校正的 Rice-Ramsperger-Kassel-Marcus 理论确定了温度和压力依赖的速率常数。结果表明，在 Ar 压力为 100 Torr 和温度范围为 T < 700 K（在 P = 700 Torr 时以 N2 为浴气，T ≤ 900 K）下，通过碰撞稳定化形成的 IM1（CF(3)CHCH(2)OH）和 IM2（CF(3)CHOHCH(2)）是主要产物，而通过加成/消除途径生成的 CH(2)═CHOH 和 CF(3)是在 700-2000 K 温度范围内的主要终产物。在 T ≥ 2000 K 时，通过氢消除生成的 CF(3)CHCH 和 CF(3)CCH(2)的生成变得重要。计算结果与可用的实验数据吻合良好。本理论研究有助于理解 CF(3)CH═CH(2) + OH 反应的特性。
