Isotope-Dependent Rotational States Distributions Enhanced by Dynamic Resonance States: A Comparison Study of the F + HD → HF(vHF = 2) + D and F + H2 → HF(vHF = 2) + H Reaction

J Phys Chem Lett. 2014 Sep 4;5(17):3049-55. doi: 10.1021/jz501460k. Epub 2014 Aug 25.

Abstract

An interesting trimodal structure in the HF (v' = 2) rotational distribution produced by the F + HD (v = 0, j = 0) reaction, but monomodal structure in the HF (v' = 2) rotational distribution produced by the F + H2 (v = 0, j = 0) reaction, were observed using a high-resolution crossed molecular beam apparatus. The rotational states of product HF (v' = 2) are much hotter in the F + HD reaction. It is uncovered that the observations are due to the dominant role of the dynamical resonance states in these two isotopic reactions. The angular potential well in the region of the resonance state of the F + HD reaction is much deeper and supports wave function with high angular kinetic energy, which in turn comes from different H tunneling processes in the F + HD and F + H2 reaction.

Keywords: Crossed Molecular Beam; F + H2 Reaction; Isotope Effects; Reaction Dynamics; Reactive Resonance; Rotational State Distribution.