Abstract
The technique of threshold photoelectron-photoion coincidence (ce:simple-paraEPICO) has been used to determine the average kinetic energy release and the kinetic energy release distributions (KERDs) for bromine atom loss from vinyl bromide (C 2 H 3 Br + ) and ethyl bromide (C 5 Br + ) ions as a function of the parent-ion internal energy. The KERDs were compared with those predicted by the statistical theory as formulated by Klots. The KERDs for the vinyl bromide ion dissociation were found to have a statistical shape between 0 and 2 eV above the dissociation limit. On the other hand, the KERDs for the ethyl bromide ion dissociation were statistical only in the region of the ground electronic state. Ions prepared in the A¯ state have KERDs characteristic of a direct dissociation. This indicates that the direct dissociation rate is faster than the rate of radiationless transition to the ground electronic state.
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