A quasiclassical trajectory and quantum mechanical study of the O(D-1)+D-2 reaction dynamics. Comparison with high resolution molecular beam experiments

摘要

A theoretical study of the dynamics of the O(1D) + D2 reaction has been performed at the collision energies (Ec¼ 86.7 meV and 138.8 meV) of a recent high resolution molecular beam experiment using the D-atom Rydberg ‘‘ tagging’’ technique (X. Liu et al., Phys. Rev. Lett., 2001, 86, 408). The theoretical calculations havebeen carried out on the ab initio 11A0, 11A00 and 21A0potential energy surfaces (PES) by Dobbyn and Knowles.The quasiclassical trajectory (QCT) method was used for the investigation on the ground electronic PES (11A0).Non-adiabatic transitions between this PES and the excited 21 A0 were considered by using a trajectory surface hopping methodology. An accurate quantum mechanical (QM) approach was used for the reaction on the excited 11A0PES. The theoretical results are globally in good agreement with the measurements and indicate that, although the excited 11A00 surface does contribute to the reaction at the higher collision energy, a large part of the observed increase in backward reactive scattering is due to the reaction over the ground state 11 A0PES.