Trajectory Surface Hopping Approach to Nonadiabatic Molecular Collisions: The Reaction of H+ with D2

TLDR

The study proposes an extension of classical trajectory methods to handle nonadiabatic molecular collisions. The method models nuclei classically on a single potential surface, then splits trajectories at nonadiabatic regions into branches on different surfaces, and is applied to a 3‑D trajectory surface‑hopping simulation of H⁺ + D₂ at 4 eV. The approach shows excellent agreement with experiment, indicating its potential usefulness.

Abstract

An extension of the classical trajectory approach is proposed that may be useful in treating many types of nonadiabatic molecular collisions. Nuclei are assumed to move classically on a single potential energy surface until an avoided surface crossing or other region of large nonadiabatic coupling is reached. At such points the trajectory is split into two branches, each of which follows a different potential surface. The validity of this model as applied to the HD2+ system is assessed by numerical integration of the appropriate semiclassical equations. A 3d “trajectory surface hopping” treatment of the reaction of H+ with D2 at a collision energy of 4 eV is reported. The excellent agreement with experiment is an encouraging indication of the potential usefulness of this approach.