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The reaction Cl + isobutene (i-C 4 H 8 ) was reported by Suits  et al . to proceed via, in addition to abstraction, an addition-elimination path following a roaming excursion of Cl; a near-zero translational energy release and an isotropic angular distribution observed at a small collision energy characterized this mechanism. We employed a new experimental method to further characterize this roaming mechanism through observation of the internal distribution of HCl ( v, J ) and their temporal behavior upon irradiation of a mixture of Cl 2 C 2 O 2  and  i -C 4 H 8  in He or Ar buffer gas. With 1–3 Torr buffer gas added to approach the condition of small collision energy, the intensities of emission of HCl ( v  = 1, 2) and the HCl production rates increased significantly; Ar shows a more significant effect than He because Ar quenches Cl more efficiently to reduce the collisional energy and facilitate the roaming path. According to kinetic modeling, the rate of addition-elimination (roaming) increased from  k  E  ≈ 2 × 10 5  s −1  when little buffer gas was present to ~1.9 × 10 6  s −1  when 2–3 Torr of Ar was added, and the branching ratio for formation of [HCl ( v  = 2)]/[HCl ( v  = 1)] increased from 0.02 ± 0.01 for abstraction to 0.06 ± 0.01 for roaming.

New experimental evidence to support roaming in the reaction Cl + isobutene (i-C4H8)