A theoretical study on the mechanism and dynamics of reactions (CF3)2CHOCH2F/(CF3)2CHOCHF2 with OH radical
Abstract
The information related with the mechanism of reactions (CF3)2CHOCH2F + OH (R1) and (CF3)2CHOCHF2 + OH (R2) was explored theoretically at the BMC-CCSD//BMK/6-311 + G(d,p) level. Based on the optimised structures, energies, and other information, the rate constants were evaluated by the canonical variational transition-state theory with small curvature tunneling contributions in a temperature range of 220-2000 K. For each reaction, there are both hydrogen-abstraction and displacement channels. In addition, more than one hydrogen atom can be abstracted. The relationship between hydrogen abstraction and displacement, between different hydrogen-abstraction channels, and between reactions R1 and R2 are elucidated.
- Publication:
-
Molecular Physics
- Pub Date:
- November 2014
- DOI:
- 10.1080/00268976.2014.925148
- Bibcode:
- 2014MolPh.112.2987W
- Keywords:
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- density functional theory;
- direct dynamics method;
- rate constants