Using quantum dynamics to study the effect of energy efficiency on the reactivity of the OH + DBr reaction

Abstract

We report a time-dependent, full dimensional, wave-packet calculation for the reaction of OH + DBr to examine the effect of the energy efficiency on the reactivity. This study shows that the vibrational excitations of the OH and DBr enhance the reaction. However, the rotational excitations of OH and DBr both hinder the reaction. As a result, the vibrational energies of both the OH and DBr reactants are more efficient at promoting the reactivity than the translational energy, while the rotational energies of OH and DBr are less effective than the translational energy. By analyzing the state population of the vibrational and rotational states along the reaction pathway, we also developed an approach in order to explain the enhancement of the vibrational excitation and the hindrance of the rotational excitation of the reaction. We found that the initial-state selected vibrational excited states of OH and DBr are the dominant components, respectively, for surmounting the barrier. However, the initial-state selected rotational excited states of OH and DBr are no longer the dominant states for surmounting the transition state owing to their population changes in the van der Waals well. This quantitative analysis demonstrates the potential well in the entrance valley plays an important role in the energy efficiency with regards to the reactivity.