Ab initio study on the thermolysis of β-hydroxyolefins in gas phase

摘要

Thermolysis studies of β-hydroxyolefins in gas phase were realized using ab initio MP2 and DFT methods at the 6-31G~* levels to explore the possibility of determining a possible concerted process with a six-membered cyclic transition state (TS). Vibrational frequency calculations were carried out in order to confirm the stationary states, including TS structures. IRC calculations have been performed in all cases in order to verify that localized TS structures connect with the corresponding minimum stationary points associated with the reactant and products. With the aim of corroborating the postulated mechanism in the experimental study, we present a theoretical study in order to calculate the rate constants and the activation parameters. The results obtained are in accordance with the experimental conclusions.