A combined experimental and computational study on the reaction dynamics of the 1-propynyl radical (CH3CC; X2A1) with ethylene (H2CCH2; X1A1g) and the formation of 1-penten-3-yne (CH2CHCCCH3; X1A′)

Abstract

The crossed molecular beam reactions of the 1-propynyl radical (CH₃CC; X²A₁) with ethylene (H₂CCH₂; X¹A_1g) and ethylene-d₄ (D₂CCD₂; X¹A_1g) were performed at collision energies of 31 kJ mol⁻¹ under single collision conditions. Combining our laboratory data with ab initio electronic structure and statistical Rice–Ramsperger–Kassel–Marcus (RRKM) calculations, we reveal that the reaction is initiated by the barrierless addition of the 1-propynyl radical to the π-electron density of the unsaturated hydrocarbon of ethylene leading to a doublet C₅H₇ intermediate(s) with a life time(s) longer than the rotation period(s). The reaction eventually produces 1-penten-3-yne (p1) plus a hydrogen atom with an overall reaction exoergicity of 111 ± 16 kJ mol⁻¹. About 35% of p1 originates from the initial collision complex followed by C–H bond rupture via a tight exit transition state located 22 kJ mol⁻¹ above the separated products. The collision complex (i1) can also undergo a [1,2] hydrogen atom shift to the CH₃CHCCCH₃ intermediate (i2) prior to a hydrogen atom release; RRKM calculations suggest that this pathway contributes to about 65% of p1. In higher density environments such as in combustion flames and circumstellar envelopes of carbon stars close to the central star, 1-penten-3-yne (p1) may eventually form the cyclopentadiene (c-C₅H₆) isomer via hydrogen atom assisted isomerization followed by hydrogen abstraction to the cyclopentadienyl radical (c-C₅H₅) as an important pathway to key precursors to polycyclic aromatic hydrocarbons (PAHs) and to carbonaceous nanoparticles.