Analytical potential energy surface and dynamics for the OH + CH3OH reaction

Using as functional form a combination of valence bond and mechanic molecular terms a new full-dimensional potential energy surface was developed for the title reaction, named PES-2022, which was fitted to high-level ab initio calculations at the coupled-cluster singles, doubles, and perturbative triples-F12 explicitly correlated level on a representative number of points describing the reactive system. This surface simultaneously describes the two reaction channels, hydrogen abstraction from the methyl group [(R1) path] and from the alcohol group [(R2) path] of methanol to form water. PES-2022 is a smooth and continuous surface, which reasonably describes the topology of this reactive system from reactants to products, including the intermediate complexes present in the system. Based on PES-2022 an exhaustive dynamics study was performed using quasi-classical trajectory calculations under two different initial conditions: at a fixed room temperature, for direct comparison with the experimental evidence and at different collision energies, to analyze possible mechanisms of reaction. In the first case, the available energy was mostly deposited as water vibrational energy, with the vibrational population inverted in the stretching modes and not inverted in the bending modes, reproducing the experimental evidence. In the second case, the analysis of different dynamics magnitudes (excitation functions, product energy partitioning, and product scattering distributions), allows us to suggest different mechanisms for both (R1) and (R2) paths: a direct mechanism for the (R2) path vs an indirect one, related with nearly trapped trajectories in the intermediate complexes, for the (R1) path.

Automated summary

A new full-dimensional potential energy surface, PES-2022, was developed for the title reaction. It accurately describes the reactive system of methanol, including both hydrogen abstraction reaction channels. Based on PES-2022, a comprehensive dynamics study was conducted to analyze the reaction mechanisms under different conditions.