Calculation of the state-to-state S-matrix for tetra-atomic reactions with transition-state wave packets: H_2/D_2 + OH → H/D + H_2O/HOD

摘要

This work is concerned with the calculation of state-to-state S-matrix elements for four-atom reactions using a recently proposed method based on the quantum transition-state theory. In this approach, the S-matrix elements are computed from the thermal flux cross-correlation functions obtained in both the reactant and product arrangement channels. Since transition-state wave packets are propagated with only single arrangement channels, the bases/grids required are significantly smaller than those needed in state-to-state approaches based on a single set of scattering coordinates. Furthermore, the propagation of multiple transition-state wave packets can be carried out in parallel. This method is demonstrated for the H_2/D_2 + OH → H/D + H_2O/HOD reactions (J = 0) and the reaction probabilities are in excellent agreement with benchmark results.