We have conducted a combined experimental and theoretical study on the formation of distinct isomers of resonantly stabilized free radicals, C4H3, which are important intermediates in the formation of polycyclic aromatic hydrocarbons in combustion flames and possibly in the interstellar medium. Our study utilized laser ablation of graphite in combination with seeding the ablated species in neat methylacetylene gas which also acted as a reagent. Photoionization efficiency (PIE) curves were recorded of the C4H3 isomers at the Advanced Light Source from 8.0 to 10.3 eV. The experimental PIE curve was compared with theoretical ones suggesting the formation of four C4H3 radicals: two acyclic structures i-C4H3 [1] and E/Z-n-C4H3 [2E/2Z]and two cyclic isomers 3 and 4. These molecules are likely formed via an initial addition of ground state carbon atoms to the carbon-carbon triple bond of the methylacetylene molecule followed by isomerization via hydrogen migrations and ring opening and emission of atomic hydrogen from these intermediates
