Reaction dynamics of oxygen atoms with unsaturated hydrocarbons from crossed molecular beam studies: primary products, branching ratios and role of intersystem crossing

Abstract

We review the progress made in the understanding of the dynamics of the reactions of ground state oxygen atoms, O(3P), with unsaturated hydrocarbons (acetylene, ethylene, allene, propyne and propene) which are of great relevance, besides from a fundamental point of view, in combustion chemistry and of interest also in atmosphere- and astro-chemistry. Advances in this area have been made possible by an improved crossed molecular beams (CMBs) instrument with rotating mass spectrometric detection and time-of-flight analysis which features product detection by low-energy electron soft-ionisation for increased sensitivity and universal detection power. This apparatus offers the capability of identifying virtually all primary reaction channels, characterising the dynamics, and determining the branching ratios (BRs) for these polyatomic multichannel nonadiabatic reactions. The reactive scattering results are rationalised with the assistance of theoretical information from other laboratories on the stationary points and product energetics of the relevant ab initio potential energy surfaces (PESs). For the simpler prototypical systems, such as O(3P) + ethylene, detailed comparisons with synergic state-of-the-art quasiclassical trajectory surface-hopping calculations on full dimensional ab initio coupled triplet and singlet PESs have recently been possible. For more complex systems, such as O(3P) + propene, comparisons with the results of synergic statistical calculations of BRs on ab initio coupled triplet and singlet PESs, have also been carried out very recently. The combined experimental/theoretical approach has allowed for a better understanding of the mechanism of these reactions. And overall has deepened considerably our understanding of chemical reactivity; in addition, these studies provide an important bridge between CMBs dynamics and thermal kinetics as well as valuable information for improving combustion and astrochemistry models.