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On the kinetic mechanism of reactions of hydroxyl radical with CHF CH F (n = 1-3)

Theoretical Chemistry Accounts, ISSN: 1432-881X, Vol: 118, Issue: 2, Page: 315-323
2007
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The potential energy surfaces of the reactions CHFCH F (n = 1-3) + OH were investigated by MPWB1K and BMC-CCSD (single-point) methods. Furthermore, with the aid of canonical variational transition state theory including the small-curvature tunneling correction, the rate constants of the title reactions were calculated over a wide temperature range of 220-1,500 K. Agreement between the CVT/SCT rate constants and the experimental values is good. Our results show that the order of rate constants is CHFCHF + OH > CHF CHF + OH > CHFCF + OH. For reaction CHFCHF + OH, the 1-H-abstraction channel dominates the reaction at the whole temperature, while 2-H-abstraction channel appears to be competitive with the increase of temperature. © 2007 Springer-Verlag.

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