Three-dimensional wave packet dynamics of H2 + D2 reaction

Initial state selected time-dependent wave packet calculations were carried out for the H-2(v(1) = high) + D-2(v(2) = low) reaction within a three degrees of freedom model. The probabilities for different competitive processes were studied on two realistic global potential energy surfaces (PESs) - BMKP and ASP. The orientation of the cold diatom did not greatly affect the reaction processes, while the orientation of the hot diatom had a significant effect. The BMKP surface generally gave lower energy thresholds than the ASP surface, except for the collision induced dissociation (CID) within the T-II geometry where the hot diatom comes in head-on perpendicular to the cold diatom. Isotopic substitution effects were studied on the recent BMKP PES. The H-2 + D-2 reaction was more effective for CID and showed more structured probability curves for single exchange reaction (SE) and three-body complex formation (3BC) than the H-2 + H-2 reaction. (C) 2011 Elsevier B. V. All rights reserved.