Direct ab initio dynamics calculations of the rate constants for the reaction of CHF2CF2OCH3 with Cl

• Published in: International journal of chemical kinetics 2007-04, Vol.39 (4), p.221-230
• Main Authors: Yang, Lei, He, Hong-Qing, Ji, Yue-Meng, Liu, Jing-Yao, Li, Ze-Sheng
• Format: Article
• Language: English
• ISSN: 0538-8066; 1097-4601
• DOI: 10.1002/kin.20230

A dual‐level direct dynamics method is employed to reveal the dynamical properties of the reaction of CHF2CF2OCH3 (HFE‐254pc) with Cl atoms. The optimized geometries and frequencies of the stationary points and the minimum energy path (MEP) are calculated at the B3LYP/6‐311G(d,p) level by using GAUSSIAN 98 program package, and energetic information is further refined by the G3(MP2) method. Two H‐ion channels have been identified. For the reactant CHF2CF2OCH3 and the two products, CHF2CF2OCH2 and CF2CF2OCH3, the standard enthalpies of formation are evaluated with the values of −256.71 ± 0.88, −207.79 ± 0.12, and −233.43 ± 0.88 kcal/mol, respectively, via group‐balanced isodesmic reactions. The rate constants of the two reaction channels are evaluated by means of canonical variational transition‐state theory (CVT) including the small‐curvature tunneling (SCT) correction over a wide range of temperature from 200 to 2000 K. The calculated rate constants agree well with the experimental data, and the Arrhenius expressions for the title reaction are fitted and can be expressed as k1 = 9.22 × 10−19 T2.06 exp(219/T), k2 = 4.45 × 10−14 T0.90 exp(−2220/T), and k = 4.71 × 10−22 T3.20) exp(543/T) cm3 molecule−1 s−1. Our results indicate that H‐ion from CH3 group is the main reaction pathway in the lower temperature range, while H‐ion from CHF2 group becomes more competitive in the higher temperature range. © 2007 Wiley Periodicals, Inc. 39: 221–230, 2007