A theoretical study on the reaction mechanisms of O(~3P)+1-butene

摘要

The reaction of O(~3P) with 1-butene (CH _3CH _2CHi=CH _2) are examined by applying the UMP2 and G3 methods. The minimum energy crossing points (MECPs) between the singlet and triplet potential energy surfaces are located using the Newton-Lagrange method, and it is shown that the MECPs play a key role in the reaction mechanisms. The complex reaction mechanisms are revealed for both adiabatic and nonadiabatic reaction channels, and the observations in several recent experiments can be rationalized based upon the present calculations. The calculational results indicate that the site selectivity of the addition of O(~3P) to either carbon atom of the double bond of 1-butene is not remarkable. In addition, the formation mechanisms of butenols are discussed. The butenols can be created not only by the keto-enol tautomerization, but also by the rearrangement and decomposition reaction involving the epoxy compound.