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Poster De Conférence Année : 2014

Chlorine Addition/elimination to Butenes Exclusively Proceeds via Roaming

Résumé

We present a crossed-beam dc slice imaging study of the reactions of chlorine atom with selected unsaturated hydrocarbons. Single-photon ionization at 157nm is used to record the velocity-flux contour maps of the radical products at various collision energies in single-collision conditions. These experimental investigations are augmented with ab initio calculations which, taken together, reveal trends in product energy and angular momentum partitioning and offer deep insight into the reaction mechanisms. By focusing on a series of butene isomer targets, we show that the differential cross-sections corresponding to the formation of HCl and alkenyl radicals reflect the competition between direct and indirect reactions, the latter being mediated by Cl addition prior to HCl elimination. A careful analysis of the potential energy surfaces show that, to decompose, the highly frustrated π adducts must undergo near-dissociation before eliminating HCl at the adjacent saturated sites. Hence, our results suggest that roaming radical dynamics, now widely recognized in unimolecular reactions, may play a central role in a broad class of bimolecular reactions as well.
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Dates et versions

hal-01246957 , version 1 (21-12-2015)

Identifiants

  • HAL Id : hal-01246957 , version 1

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Yuanyuan Shi, Alexander Kamasah, Baptiste Joalland, Arthur G. Suits, Alexander M. Mebel. Chlorine Addition/elimination to Butenes Exclusively Proceeds via Roaming. Atomic and Molecular Interactions, Gordon Research Conference, Jul 2014, Stonehill College, MA, United States. ⟨hal-01246957⟩
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