Exact quantum calculations of the kinetic isotope effect: Cross sections and rate constants for the F+HD reaction and role of tunneling

Abstract

In this paper we present integral cross sections (in the 5-220 meV collision energy range) and rate constants (in the 100-300 K range of temperature) for the F+HD reaction leading to HF+D and DF+H. The exact quantum reactive scattering calculations were carried out using the hyperquantization algorithm on an improved potential energy surface which incorporates the effects of open shell and fine structure of the fluorine atom in the entrance channel. The results reproduce satisfactorily molecular beam scattering experiments as well as chemical kinetics data for both the HF and DF channels. In particular, the agreement of the rate coefficients and the vibrational branching ratios with experimental measurements is improved with respect to previous studies. At thermal and subthermal energies, the rates are greatly influenced by tunneling through the reaction barrier. Therefore exchange of deuterium is shown to be penalized with respect to exchange of hydrogen, and the isotopic branching exhibits a strong dependence on translational energy. Also, it is found that rotational excitation of the reactant HD molecule enhances the production of HF and decreases the reactivity at the D end, obtaining insight on the reaction stereodynamics.