Ab Initio and Quasiclassical Trajectory Study of the O(3P) + 2-Propanol Hydrogen Abstraction Reaction.

Abstract

We present a theoretical study of the hydrogen abstraction reaction from 2-propanol by ground-state oxygen atoms. First, ab initio calculations are used to characterize the stationary points of the potential energy surface. Rotation around the C-C-O-H dihedral affords two conformers in 2-propanol, which gives rise to 13 hydrogen abstraction reaction pathways grouped into three channels, Cα, Cβ, and O, depending on the abstraction site. Reaction at Cα exhibits the lowest barrier and largest exothermicity, followed by reaction at Cβ, and at 2-propanol's oxygen atom. Additional ab initio calculations beyond the stationary points are employed to obtain a grid of energies with which a specific-reaction-parameters (SRP) PM6 semiemipirical Hamiltonian is derived for the title reaction. The SRP-PM6 model captures the energetics of the reaction with higher accuracy than some conventional first-principles methods but is efficient enough to allow for extensive reaction dynamics calculations. Quasiclassical trajectories are subsequently propagated with the SRP-PM6 Hamiltonian to obtain reaction dynamics properties that are compared to experiments. Product translational energy and angular distributions for reaction at Cα with the two conformers of 2-propanol are in good agreement with recent molecular-beam measurements, and they exhibit largely backward scattering with modest energy release to relative translation. Most of the energy is deposited into the organic product, substantiating a reaction mechanism dominated by rebound dynamics.