Mechanistic and Kinetic Study of CF3CH=CH2 + OH Reaction

作者：Zhang, Yunju; Sun, Jingyu; Chao, Kai; Sun, Hao; Wang, Fang; Tang, ShuWei; Pan, Xiumei; Zhang, Jingping; Wang, Rongshun^*

来源：Journal of Physical Chemistry A, 2012, 116(12): 3172-3181.

DOI：10.1021/jp209960c

• AB-INITIO
• OH RADICALS
• ATMOSPHERIC CHEMISTRY
• RATE CONSTANTS
• CL ATOMS
• CF3CF=CH2
• PRODUCTS

The potential energy surfaces of the CF3CH=CH2 + 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 (CF3CHCH2OH) and IM2 (CF3CHOHCH2) 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 CH2=CHOH and CF3 produced by the addition/elimination pathway are the dominant end products at 700-2000 K. The production of CF3CHCH and CF3CCH2 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 CF3CH=CH2 + OH.

• 出版日期2012-3-29
• 单位吉林大学; 东北师范大学