Translational, vibrational, rotational enhancements and alignments of reactions H + ClF (v= 0–5,j= 0,3,6,9) → HCl + F and HF + Cl, atE_rel= 0.5–20 kcal/mol

Abstract

Quasi-classical trajectory calculations of the title reactions H + ClF (v = 0–5, j = 0,3,6,9) → HCl + F and H + ClF (v = 0–5, j = 0,3,6,9) → HF + Cl at Erel = 0.5 kcal/mol–20 kcal/mol on ground potential energy surface DHTSN of 1 2A′ [M. P. Deskevich, M. Y. Hayes, K. Takahashi, R. T. Skodje and D. J. Nesbitt, J. Chem. Phys. 124, 224303 (2006)] are performed. Potential energy surfaces derived from DHTSN for the title reactions are obtained, and compared with that of DHTSN for the reaction F + HCl → HF + Cl. Both potential energy surfaces have an early barrier pattern. Integral cross sections and alignments of product molecules HCl and HF dependent on the internal energy states v and j of reactant molecule ClF are obtained and compared. Translational, vibrational, and rotational energy specific translational enhancements of the reactant molecule ClF of the title reactions are found. Reaction mechanisms of the title reactions according to the respective potential energy contours are further found and explained. Reasons of simultaneous translational and vibrational enhancements are clarified.