Theoretical study of a reaction mechanism of tropospheric interest: CH 3 CH 2 F + OH

• Published in: Progress in reaction kinetics and mechanism Vol. 38; no. 4; pp. 342 - 358
• Main Authors: Wang, Hongliang, Wang, Bingxing, Wang, Bingli, Yang, Bing
• Format: Journal Article
• Language: English
• Published: 01.12.2013
• ISSN: 1468-6783; 1471-406X
• DOI: 10.3184/146867813X13744829848125

Dual-level electronic structure calculation has been performed to investigate the mechanism and all possible channels of OH radical reaction with CH 3 CH 2 F. Geometries and frequencies are computed at the B3LYP/6-311G(d,p) level of theory for all stationary points and complexes and transition states are located. Potential energy surfaces are constructed at the PMP2/cc-pVTZ//B3LYP/6-311G(d,p) level + ZPE correction. Four types of reaction channels are identified: hydrogen abstraction, fluorine abstraction and attack on carbon atom along or perpendicular to the C–C bond axis. Hydrogen abstraction channels have lower barriers and are more exothermic, while out-of-plane β–H abstraction with the lowest barrier is competitive with a–H abstraction. Due to the high energy barrier, contributions of non-H abstraction channels are excluded. The influence of hydrogen bonding interaction is clearly observed in the barrier heights.