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,* email, 3,4email and 5email
Received: 16 May 2013; in revised form: 18 June 2013 / Accepted: 20 June 2013 / Published: 4 July 2013
(This article belongs to the Special Issue Computational Chemistry)
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.
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
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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.

AMA 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(7):7873-7885.

Chicago/Turabian Style

Zhang, Meiling; Song, Ce; Tian, Yan. 2013. "Comprehensive Theoretical Studies on the Reaction of 1-Bromo-3,3,3-trifluoropropene with OH Free Radicals." Molecules 18, no. 7: 7873-7885.

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