Direct comparison of 3-centre and 4-centre HBr elimination pathways in methyl-substituted vinyl bromidesElectronic supplementary information (ESI) available: Calculations of rates of methyl migration in the energized, ground state molecules; VMI results and analysis of Br and Br channels from 193 nm photolysis of the vinyl bromide derivatives; HBr v and J dependence of TKER distributions; results from HBr (v = 0) detection using the g-X REMPI transition. All experimental and computational data a

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. HBr elimination from energized methyl vinyl bromide molecules can occur through competing 3- and 4-centre transition states.