Don’t forget the trans: double bond isomerism radical-acetylene growth reactions affect the primary stages of PAH and soot formation

Abstract

In combustion, acetylene is a key species in molecular-weight growth reactions that form polycyclic aromatic hydrocarbons (PAHs) and ultimately soot particles. Radical addition to acetylene generates a vinyl radical intermediate, which has both trans and cis isomers. This isomerism can lead to profound changes in product distributions that are as yet insufficiently investigated. Herein, we explore acetylene addition to substituted trans-vinyl radicals, including potential rearrangement to cis structures, for eight combustion-related hydrocarbon radicals calculated using a composite method (G3X-K). Of these eight systems, the phenyl trans- and cis-Bittner-Howard HACA (hydrogen abstraction, C2..