Theoretical Study and Rate Constant Computation on the Reaction HFCO + OH → CFO + H2O

Abstract

The potential energy surface, including the geometries and frequencies of the stationary points, of the reaction HFCO + OH is calculated using the MP2 method with 6-31+G(d,p) basis set, which shows that the direct hydrogen abstraction route is the most dominating channel with respect to addition and substitution channels. For the hydrogen abstraction reaction, the single-point energies are refined at the QCISD(T) method with 6-311++G(2df,2pd) basis set. The calculated standard reaction enthalpy and barrier height are -17.1 and 4.9 kcal mol(-1), respectively, at the QCISD(T)/6-311++G(2df,2pd)//MP2/6-31+G(d,p) level of theory. The reaction rate constants within 250-2500 K are calculated by the improved canonical variational transition state theory (ICVT) with small-curvature tunneling (SCT) correction at the QCISD(T)/6-311++G(2df,2pd)//MP2/6-31+G(d,p) level of theory. The fitted three-parameter formula is k = 2.875 x 10(-13) (T/1000)1.85 exp(-325.0/T) cm(3) molecule(-1) s(-1). The results indicate that the calculated ICVT/SCT rate constant is in agreement with the experimental data, and the tunneling effect in the lower temperature range plays an important role in computing the reaction rate constants.