Dynamics of OH Production in the Reaction of O(¹D₂) with Cyclopropane

Abstract

The OH(X 2 Π, υ" = 0,1) internal state distribution following the reaction of electronically excited oxygen atom (O( 1 D2)) with cyclo-C3H6 has been measured using laser-induced fluorescence, and compared with that following the reaction of O( 1 D2) with C3H8. The overall characteristics of the OH internal energy distributions for both reactions were qualitatively similar. The population propensity of the П(A′) Λ-doublet sub-level suggested that both reactions proceeded via an insertion/elimination mechanism. Bimodal rotational population distributions supported the existence of two parallel mechanisms for OH production, i.e., statistical insertion and nonstatistical insertion. However, detailed analysis revealed that, despite the higher exoergicity of the reaction, the rotational distribution of the OH following the reaction of O( 1 D2) with C3H8 was significantly cooler than that with cyclo-C3H6, especially in the vibrational ground state. This observation was interpreted as the effect of the flexibility of the insertion complex and faster intramolecular vibrational relaxation (IVR).