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

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, C alpha, C beta, and O, depending on the abstraction site. Reaction at C alpha exhibits the lowest barrier and largest exothermicity, followed by reaction at C beta, 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 C alpha 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.