Trajectory studies of the reaction F−+HCl→HF+Cl−. I. Reaction rate constant

Abstract

Ab initio calculations at the MP4/6–31G** level in conjunction with experimental data were used to derive an analytical potential energy function for the reaction F−+HCl→HF+Cl−. A Monte Carlo-classical trajectory method was used to estimate the thermal energy reaction rate constants at various temperatures. The results showed that the reaction efficiency decreases sharply as temperature increases. At room temperature, the calculated reaction rate constant is in excellent agreement with the experimental result. Reaction rate constants were also calculated as a function of relative translational energy at internal (vibrational and rotational) temperatures of 50, 300, and 3000 K. It was observed that the rate constant exhibits a similar relative translational energy dependence as the temperature dependence. Calculated results show no internal temperature dependence of the reaction rate constant.