Vibrational Enhancement Factor of the Cl + CHD3(v1 = 1) Reaction: Rotational-Probe Effects.

The vibrational enhancement factor in the Cl + CHD3(v1 = 1) reaction is revisited over the collisional energy range of 2–5.9 kcal mol–1. Contrary to the previous results obtained by probing the low-|N, K⟩ states of CD3(v = 0) products, CH stretching excitation becomes more efficacious than the same amount of translational energy in promoting the HCl(v) + CD3(v = 0) product pairs when all-|N, K⟩ states are probed. Whereas the new vibrational enhancement factors, which are three to four times larger than the previous report, agree reasonably well with a recent reduced-dimensionality quantum dynamics calculation, a cautious note is made on the different initial |J,K⟩ rotational selections of the CHD3 reactants in the present theory–experiment comparison.