Variation of kinetic energy release and average internal energy with temperature and electron energy for unimolecular ionic transitions

The kinetic energy released and the intensity ratios [m*]/[M]+ or [m*]/[F]+ (where m* is a metastable peak, and [M]+ and [F]+ are molecular‐ion and fragment‐ion peaks, respectively) for seven unimolecular ionic transitions generated from benzyl alcohol and benzylamine have been studied as a function of ion‐source temperature and ionizing electron energy. Only during HCN elimination from [C7H8N]+ fragment ion does the kinetic energy released and the intensity ratio [58.9]/[106]+ display a temperature dependence. On the other hand, the kinetic energy released during only two transitions, generated from benzyl alcohol, displays a significant electron‐energy dependence while the intensity ratios [m*]/[M]+ or [m*]/[F]+ for all the transitions studied exhibit marked decrease with decreasing electron energy starting at about 40 eV.