Full-dimensional time-dependent wave packet dynamics of H2 + D2 reaction

摘要

Collision induced dissociation (CID), four center reaction (4C), and single exchange reaction (SE) in H2 (v1 = high) + D2 (v2 = low) were studied by means of time-dependent wave packet approach within a full-dimensional model. Initial state-selected total reaction probabilities for the three competitive processes have been computed on two realistic global potential energy surfaces of Aguado-Suárez-Paniagua and Boothroyd-Martin-Keogh-Peterson (BMKP) with the total angular momentum J = 0. The role of both vibrationally excited and rotationally excited reagents was examined by varying the initial vibrational and rotational states. The vibrational excitation of the hot diatom gives an enhancement effect on the CID process, while the vibrational excitation of the cold diatom gives an inhibition effect. The rotational excitation of both reagents has a significant effect on the reaction process. The 4C and SE probabilities are at least one order of magnitude smaller than the CID probabilities over the energy range considered. Isotope substitution effects were also studied by substituting the collider D2 by H2 and HD on the BMKP potential energy surfaces. The CID process is most efficient for the H2 + D2 combination and least efficient for the H2 + H2 combination and is different for the 4C and SE processes. © 2011 American Institute of Physics Article Outline INTRODUCTION THEORY RESULTS Extraction of 4C, CID, and SE reaction probabilities Effect of vibrational energy Effect of rotational energy Isotope substitution effect CONCLUSIONS