Theoretical Study on the Mechanism of the Gas-phase Reaction of Sc+ with Propargyl Alcohol
Abstract
In order to elucidate the reaction mechanisms of reaction Sc+ with propargyl alcohol (PPA), the triplet potential energy surface for the reactions has been theoretically investigated using a DFT method. The geometries for the reactants, intermediates, transition states and products were completely optimized at B3LYP/DZVP level. The single point energy of each stationary point was calculated at MP4/(6-311+G∗︁ ∗︁ for C, H, O and Lanl2dz for Sc+) level. All the transition states were verified by the vibrational analysis and the internal reaction coordinate (IRC) calculations. The present results show that the reaction takes an insertion-elimination mechanism both along the OH and CO bond activation branches, but the CO bond activation is much more favorable in energy than the OH bond activation. All theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction.
