A comparative study of hydrogen-atom release dynamics in radical-radical reactions

Abstract

This paper presents a comparative study of the atomic hydrogen release dynamics in the oxidation reactions of saturated and unsaturated hydrocarbon radicals. The prototypal radical-radical reactive scattering processes were examined by applying a combination of crossed beams and high-resolution vacuum-ultraviolet laser-induced fluorescence spectroscopy. With the aid of ab initio and statistical calculations, remarkable dynamic features were uncovered in the Doppler profile analysis of the atomic hydrogen products. The difference in the reactivity of saturated and unsaturated hydrocarbon radicals could be rationalized in terms of the characteristic geometry of the transition state and activation barriers along the exit channel on the doublet potential energy surface.