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Direct and Indirect Hydrogen Abstraction in Cl plus Alkene Reactions

Research output: Contribution to journalArticle

Original languageEnglish
Pages (from-to)5595-5607
Number of pages13
JournalJournal of Physical Chemistry A
Volume118
Issue number30
Early online date10 Jun 2014
DOIs
DateE-pub ahead of print - 10 Jun 2014
DatePublished (current) - 31 Jul 2014

Abstract

Reactions between Cl atoms and propene can lead to HCl formation either by direct H abstraction or through a chloropropyl addition complex. Barring stabilizing collisions, the chloropropyl radical will either decompose to reactants or form HCl and allyl products. Using velocity-map imaging to measure the quantum state and velocity of the HCl products provides a view into the reaction dynamics, which show signs of both direct and indirect reaction mechanisms. Simulated trajectories of the reaction highlight the role of the direct H-abstraction pathways, and the resultant simulated scattering images show reasonable agreement with measurement. The simulations also show the importance of large excursions of the Cl atom far from equilibrium geometries within the chloropropyl complex, and these large-amplitude motions are the ultimate drivers toward HCl + allyl fragmentation. Gas-phase measurements of larger alkenes, 2-methylpropene and 2,3-dimethylbut-2-ene, show slightly different product distributions but still feature similar reaction dynamics. The current suite of experiments offers ready extensions to liquid-phase bimolecular reactions.

Additional information

Accepted 10/06/2014

    Research areas

  • DIFFERENTIAL CROSS-SECTIONS, SET MODEL CHEMISTRY, REACTION DYNAMICS, MULTIPHOTON IONIZATION, CHEMICAL-DYNAMICS, ATOM REACTIONS, PRODUCT, STATE, HCL, ENERGY

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  • AlkenesMS final

    Rights statement: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal Physical Chemistry A (2014), copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/page/policy/articlesonrequest/index.html

    Accepted author manuscript, 39 MB, PDF document

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