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Direct comparison of 3-centre and 4-centre HBr elimination pathways in methyl-substituted vinyl bromides

Research output: Contribution to journalArticle

Original languageEnglish
Pages (from-to)28353-28364
Number of pages12
JournalPhysical Chemistry Chemical Physics
Issue number40
Early online date21 Sep 2016
DateAccepted/In press - 19 Sep 2016
DateE-pub ahead of print - 21 Sep 2016
DatePublished (current) - 28 Oct 2016


Elimination of HBr from UV-photoexcited vinyl bromides can occur through both 3-centre and 4-centre transition states (TSs). The competition between these pathways is examined using velocity map imaging of HBr(v=0-2, J) photofragments. The three vinyl bromides chosen for study have methyl substituents that block either the 3-centre or the 4-centre TS, or leave both pathways open. The kinetic energy distributions extracted from velocity map images of HBr from 193-nm photolysis of the three vinyl bromide compounds are approximately described by a statistical model of energy disposal among the degrees of freedom of the photoproducts, and are attributed to dissociation on the lowest electronic state of the molecule after internal conversion. Dissociation via the 4-centre TS gives greater average kinetic energy release than for the 3-centre TS pathway. The resonance enhanced multi-photon ionization (REMPI) schemes used to detect HBr restrict measurements to J ≤ 7 for v= 2 and J ≤ 15 for v=0. Within this spectroscopic range, the HBr rotational temperature is colder for the 4-centre than for the 3-centre elimination pathway. Calculations of the intrinsic reaction coordinates and RRKM calculations of HBr elimination rate coefficients provide mechanistic insights into the competition between the pathways.

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    Rights statement: This is the author accepted manuscript (AAM). The final published version (version of record) is available online via APS at DOI: 10.1039/C6CP05393A . Please refer to any applicable terms of use of the publisher.

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