Unusual differential cross sections for the H + D2O → D + HOD exchange reaction induced by the C3V transition state and quantum interference

Abstract

Previous experimental and theoretical studies have shown that direct reactive systems typically exhibit backward-peaked differential cross sections (DCS) at relatively low collision energies, while complex-forming reactive systems tend to display forward-backward symmetric DCS. Is this a universal phenomenon in all direct reactions, especially those proceeding through non-collinear transition states? In this work, we developed the quantum wave packet method to calculate the full-dimensional state-to-state DCSs for the title exchange reaction with D2O in the ground rovibrational state on a highly accurate neural network potential energy surface. For the first time, we obtain a sideward-scattered angle distribution just above the threshold, which directly reflects the C3V transition state geometry of this reaction. As the collision energy increases, the DCS broadens and undergoes a series of notable changes, culminating in the dominance of backward scattering at Ec=1.4 eV, accompanied by an early-sideward scattering peak. Although trajectory analysis can explain most of the DCS variations, significant differences persist between the quantum and quasiclassical trajectory DCSs, arising from quantum interference between the contributions from low and high partial waves. Additionally, the collision energy dependent DCSs at the scattering angle of 107° exhibit two clear step-like features around Ec=0.91 and 1.16 eV, which can be attributed to the shape resonances states trapped in the C3V well. In the energy region considered here, the majority of the available energy goes into the translational motion of the products, and the reaction exhibits low vibrational mode-specific behavior.