Nonadiabatic molecular collisions. II. A further trajectory-surface-hopping study of the ArH+2 system

Both charge transfer and chemical reaction are studied for the reactants Ar++H2, Ar+H+2, and Ar+D+2, using the trajectory-surface-hopping model with diatomics-in-molecules 2A′ surfaces for ArH+2. Results are compared with a number of recent experiments. Agreement with experiment is generally satisfactory. The reactions are direct. The Ar++H2 → ArH++H reaction is well characterized as a stripping process. Charge transfer occurs predominantly by long-range electron jump. The Ar+H+2 and Ar+D+2 cross sections depend sensitively on reactant vibration, rising sharply from v=0 to v=1, and falling gradually for v≥2. The ArH+ product is rotationally hot. Points of disagreement with experiment are discussed in the light of the approximations in the surface and the TSH model.