High vibrational excitation of the reagent transforms the late-barrier H + HOD reaction into an early-barrier reaction.

Polanyi's rules predict that a late-barrier reaction yields vibrationally cold products; however, experimental studies showed that the H2 product from the late-barrier H + H2O(|04⟩-) and H + HOD(vOH = 4) reactions is vibrationally hot. Here, we report a potential-averaged five-dimensional state-to-state quantum dynamics study for the H + HOD(vOH = 0-4) → H2 + OD reactions on a highly accurate potential energy surface with the total angular momentum J = 0. It is found that with the HOD vibration excitation increasing from vOH = 1 to 4, the product H2 becomes increasingly vibrationally excited and manifests a typical characteristic of an early barrier reaction for vOH = 3 to 4. Analysis of the scattering wave functions revealed that vibrational excitation in the breaking OH bond moves the location of dynamical saddle point from product side to reactant side, transforming the reaction into an early barrier reaction. Interestingly, pronounced oscillatory structures in the total and product vibrational-state-resolved reaction probabilities were observed for the H + HOD(vOH = 3, 4) reactions, in particular at low collision energies, which originate from the Feshbach resonance states trapped in the bending/torsion excited vibrational adiabatic potential wells in the entrance region due to van der Waals interactions.