Hydrogen-Abstraction/Acetylene-Addition Exposed.

Polycyclic aromatic hydrocarbons (PAHs) are omnipresent in the interstellar medium (ISM) and also in carbonaceous meteorites (CM) such as Murchison. However, the basic reaction routes leading to the formation of even the simplest PAH-naphthalene (C H )-via the hydrogen-abstraction/acetylene-addition (HACA) mechanism still remain ambiguous. Here, by revealing the uncharted fundamental chemistry of the styrenyl (C H ) and the ortho-vinylphenyl radicals (C H )-key transient species of the HACA mechanism-with acetylene (C H ), we provide the first solid experimental evidence on the facile formation of naphthalene in a simulated combustion environment validating the previously postulated HACA mechanism for these two radicals. This study highlights, at the molecular level spanning combustion and astrochemistry, the importance of the HACA mechanism to the formation of the prototype PAH naphthalene.