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Molecules 2013, 18(7), 7873-7885; doi:10.3390/molecules18077873
Article

Comprehensive Theoretical Studies on the Reaction of 1-Bromo-3,3,3-trifluoropropene with OH Free Radicals

1,2,* , 3,4
 and 5
1 School of Biomedical Engineering, Tianjin Medical University, Tianjin 300070, China 2 College of Basic Medical Sciences, Tianjin Medical University, Tianjin 300070, China 3 Hefei National Laboratory of Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, Anhui, China 4 Department of Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology, Stockholm SE-10691, Sweden 5 School of Science, Anhui Agricultural University, Hefei 230036, Anhui, China
* Author to whom correspondence should be addressed.
Received: 16 May 2013 / Revised: 18 June 2013 / Accepted: 20 June 2013 / Published: 4 July 2013
(This article belongs to the Special Issue Computational Chemistry)
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Abstract

The potential energy surfaces (PES) for the reaction of 1-bromo-3,3,3-trifluoropropene (CF3CHCBrH) with hydroxyl (OH) free radicals is probed theoretically at the CCSD/aug-cc-pVDZ//B3LYP/6-311++G(d,p) level of theory. All the possible stationary and first-order saddle points along the reaction paths were verified by the vibrational analysis. The calculations account for all the product channels. Based on the calculated CCSD/aug-cc-pVDZ potential energy surface, the possible reaction mechanism is discussed. Six distinct reaction pathways of 1-bromo-3,3,3-trifluoropropene (BTP) with OH are investigated. The geometries, reaction enthalpies and energy barriers are determined. Canonical transition-state theory with Wigner tunneling correction was used to predict the rate constants for the temperature range of 290–3,000 K without any artificial adjustment, and the computed rate constants for elementary channels can be accurately fitted with three-parameter Arrhenius expressions. OH addition reaction channel and the H atom abstraction channels related to the carbon-carbon double bond are found to be the main reaction channels for the reaction of 1-bromo-3,3,3-trifluoropropene (CF3CHCBrH) with hydroxyl (OH) free radicals while the products leading to CF3CHCH + BrOH and COHF2CHCBrH + F play a negligible role.
Keywords: quantum chemical calculations; reaction mechanism; transition states; potential energy surface; reaction rate constants quantum chemical calculations; reaction mechanism; transition states; potential energy surface; reaction rate constants
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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MDPI and ACS Style

Zhang, M.; Song, C.; Tian, Y. Comprehensive Theoretical Studies on the Reaction of 1-Bromo-3,3,3-trifluoropropene with OH Free Radicals. Molecules 2013, 18, 7873-7885.

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