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.

► We observed products C4H5, C4H4, C3H3 and CH3 in the reaction of C(3P) + C3H6.
► An ab initio potential-energy surface of the reaction C(3P) + C3H6 was established.
► Product isomers were identified via measurements of TOF/photoionization spectra.
► Products C4H4 and C3H3 involve exclusively HCCCHCH2 and H2CCCH, respectively.
► Branching ratios of channels C4H5 + H, C4H4 + 2H and C3H3 + CH3 were determined.