Abstract
Dual-level electronic structure calculation has been performed to investigate the mechanism and all possible channels of OH radical reaction with CH3CH2F. 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.
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