Quantum Dynamical Calculations Of The Na+HFâ†'NaF+H Reaction System

The Na+HFâ†'NaF+H reaction a prototype of metal-halide’harpooning’reaction systems has been extensively studied both experimentally and theoretically, which plays a vital role in several chemical reactions. The title reaction only containing 3 nuclei and 21 electrons enables us to calculate sufficient energy points, thus construct an accurate potential energy surface.Experimentally, Polanyi and co-workers first probed the effect on the reactivity with an increase of the reactant vibrational excitation. It turned out that there is no contribution to the reactivity for HF in the ground and first-excited vibrational states. Lee and Loesch et al drew similar conclusions.Theoretically, dynamical calculations for this reaction using quasi-classical trajectory method have been reported. However, calculations based on quantum mechanics is uncommon. It is worthwhile to mention that Gargano et al performed 3D quantum calculations for the title reaction. They investigated the energy dependence of the reactive probability for total angular momentum J=0, as well as the effect of increasing the reactant vibrational excitation.In this paper, we employing Chebyshev wave packet method perform quantum dynamical calculations on the potential energy surface constructed by Truhlar et al considering the effect of increasing the reactant vibrational excitation. Specifically, we firstly calculate the initial state-specified reaction probabilities corresponding to the total angular momentum J spanning from 0 to 120, then we obtain the integral cross sections. As a result, rate constants over the range of 0 to 1200 K are computed. Make a comparison with the experimental data we find our values match well.