CH Stretching Excitation in the Early Barrier F + CHD 3 Reaction Inhibits CH Bond Cleavage

Abstract

Shaking Prevents Breaking Intuition suggests that vibrational excitation of a molecular bond ought to increase the likelihood of its breaking in an ensuing chemical reaction. W. Zhang et al. (p. 303 ) observe precisely the opposite outcome in a spectroscopic study of the F + CHD 3 reaction. Exciting the C-H stretch leads exclusively to the formation of DF and CHD 2 products, in contrast to the more abundant yields of both HF and DF observed in the absence of CH vibration. Though the mechanism underlying this effect remains unclear, the result highlights unanticipated complexity in the reaction dynamics of a relatively simple molecule.