Mechanisms of the Ethynyl Radical Reaction with Molecular Oxygen

The ethynyl radical, ^•C₂H, is a key intermediate in the combustion of various alkynes. Once produced, the ethynyl radical will rapidly react with molecular oxygen to produce a variety of products. This research presents the first comprehensive high level theoretical study of the reaction of the ^•C₂H (²Σ⁺) radical with molecular oxygen (³Σ_g^-). Correlation methods as complete as CCSDT(Q) were used; basis sets as large as cc-pV6Z were adopted. Focal point analysis was employed to approach relative energies within the bounds of chemical accuracy (≤1 kcal mol^-1). Two dominate reaction pathways from the ethynyl peroxy radical include oxygen-oxygen cleavage from the ethynyl peroxy radical that is initially formed to produce HCCO (²A″) and O (³P) and an isomerization of the ethynyl peroxy radical to eventually yield HCO (²A') and CO (¹Σ⁺). The branching ratio between these two competitive reaction pathways was determined to be 1:1 at 298 K. Minor reaction pathways leading to the production of CO₂ (¹Σ_g⁺) and CH (²Π, ⁴Σ^-, ²Δ) were also characterized. The absence of CCO (³Σ^-) and OH (²Π) was explained in terms competition with more accessible reaction pathways.