Effects of bending excitation on the reaction dynamics of fluorine atoms with ammonia

Abstract

Vibrational excitation has been established as an efficient way to control the chemical reaction outcome. Stretching vibration of polyatomic molecules is believed to be efficient to promote abstraction reactions since energy is placed directly into the breaking bond. In this work, we report on a counterexample showing that exciting the low-frequency umbrella bending mode of ammonia enhances its reaction with fluorine atoms much more than exciting the high-frequency symmetric or asymmetric stretching mode over a wide range of collision energy, validated using both quasiclassical trajectory simulations and full-dimensional quantum dynamics calculations under the centrifugal-sudden approximation. This interesting mode-specific reaction dynamic originates from the increased chance of capturing the fluorine atom by ammonia due to the enlarged attractive interaction between them and the enhancement of the direct stripping reaction mediated by two submerged barriers.