Identification of C4H5, C4H4, C3H3 and CH3 radicals produced from the reaction of atomic carbon with propene: Implications for the atmospheres of Titan and giant planets and for the interstellar medium

We observed the products C₄H₅, C₄H₄, C₃H₃ and CH₃ of the C(³P) + C₃H₆ reaction using product time-of-flight spectroscopy and selective photoionization. The identified species arise from the product channels C₄H₅ + H, C₄H₄ + 2H and C₃H₃ + CH₃. Product isomers were identified via measurements of photoionization spectra and calculations of adiabatic ionization energy. Product C₄H₅ probably involves three isomers HCCCHCH₃, H₂CCCCH₃ and H₂CCCHCH₂. In contrast, products C₄H₄ and C₃H₃ involve exclusively HCCCHCH₂ and H₂CCCH, respectively. Reaction mechanisms are unraveled with crossed-beam experiments and quantum-chemical calculations. The ³P carbon atom attacks the π orbital of propene (C₃H₆) to form a cyclic complex c-H₂C(C)CHCH₃ that rapidly opens the ring to form H₂CCCHCH₃ followed by decomposition to HCCCHCH₃/H₂CCCCH₃/H₂CCCHCH₂ + H and H₂CCCH + CH₃; the corresponding branching ratios are 7:5:10:78 predicted with RRKM calculations at collision energy 4 kcal mol^?1. Nascent C₄H₅ with enough internal energy further decomposes to HCCCHCH₂ + H. Ratios of products C₄H₅, C₄H₄ and C₃H₃ are experimentally evaluated to be 17:8:75. This work provides a comprehensive look at product channels of the title reaction and gives implications for the formation of hydrocarbons in extra-terrestrial environments such as Titan and carbon-rich interstellar media. We suggest that the title reaction, hitherto excluded in any chemical networks, needs to be taken into account at least in the atmosphere of Titan and carbon-rich molecular clouds where rapid neutral–neutral reactions are dominant and carbon atoms and propene are abundant.