A crossed molecular beams study of the reaction of the ethynyl radical (C2H(X2Σ+)) with allene (H2CCCH2(X1A1))

Abstract

The crossed beams reaction of ground state ethynyl radicals, C₂H(X²Σ⁺), with allene, H₂CCCH₂(X¹A₁), was conducted under single collision conditions at a collision energy of 22.0 ± 0.4 kJ mol⁻¹. The center-of-mass functions were combined with earlier ab initio calculations and revealed that the reaction was barrier-less, proceeded via indirect reaction dynamics through an addition of the ethynyl radical to the terminal carbon atom of the allene molecule, and was terminated by atomic hydrogen emission via a tight exit transition state to form the ethynylallene product. The overall reaction was found to be exoergic by 93 ± 15 kJ mol⁻¹. Since the reaction is barrier-less, exoergic, and all transition states involved are located below the energy level of the separated reactants, the formation of ethynylallene is predicted to take place in low temperature atmospheres of planets and their satellites such as Titan and also in cold molecular clouds via the neutral–neutral reaction of ethynyl radicals with allene. Implications to interstellar chemistry and a comparison with the chemistry of the isoelectronic cyano radical, CN(X²Σ⁺), are also presented.