Dynamics study of the post-transition-state-bifurcation process of the (HCOOH)H+ → CO + H3O+/HCO+ + H2O dissociation: application of machine-learning techniques

Abstract

The process of protonated formic acid dissociating from the transition state was studied using ring-polymer molecular dynamics (RPMD), classical MD, and quasi-classical trajectory (QCT) simulations. Temperature had a strong influence on the branching fractions for the HCO⁺ + H₂O and CO + H₃O⁺ dissociation channels. The RPMD and classical MD simulations showed similar behavior, but the QCT dynamics were significantly different owing to the excess energies in the quasi-classical trajectories. Machine-learning analysis identified several key features in the phase information of the vibrational motions at the transition state. We found that the initial configuration and momentum of a hydrogen atom connected to a carbon atom and the shrinking coordinate of the CO bond at the transition state play a role in the dynamics of HCO⁺ + H₂O production.