A quasi-classical study in a quantum spirit of mode specificity of the H + HOD abstraction reaction.

Abstract

Quantum benchmark calculations of the H + HOD abstraction reaction [B. Zhao et al., Phys. Chem. Chem. Phys., 2018, 20, 17029-17037] provide an opportunity to test approximate methods, such as quasi-classical trajectories (QCTs) with Gaussian binning. However, the large mode-specific enhancements of this reaction lead to special challenges and unphysical QCT cross-section artifacts. We propose and apply a general backward-forward-backward (BFB) trajectory procedure to avoid cross-section artifacts arising from vibrational motion delocalization of the initially prepared reactants. We also develop and apply a general hybrid weighting scheme, in which vibrationally adiabatic products receive unit weights, while vibrationally non-adiabatic products are Gaussian weighted. Motivated by examination of the product vibrational actions, the hybrid weighting is necessary to avoid large cross-section errors. These QCTs with Gaussian weighting extensions are general and are recommended for future polyatomic reaction simulations.