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Photoelectron/photoion imaging spectrometry employing dispersed VUV radiation from the SOLEIL synchrotron has been used to study the predissociation of N 2  +  states located up to 1.3 eV above the ion's first dissociation limit. Branching ratios for unimolecular decay into either N 2  +  or N +  were obtained by measuring coincidences between threshold electrons and mass-selected product ions, using a supersonic beam of either  14 N 2  or  15 N 2  as photoionization target. The results confirm that predissociation of theC   2Σ    u    +state of  14 N 2  +  is faster than emission to the electronic ground-state by a factor 10 or more for all vibrational levels v′ ≥ 3, while for  15 N 2  +  the two decay modes have comparable probabilities for the levels v′ = 3, 4, and 5. In contrast, no significant isotope effect could be observed for the other states of N 2  +  identified in the photoelectron spectrum. For both  14 N 2  +  and  15 N 2  +  isotopologues all vibrational levels of these other states decay to an extent of at least 95% by predissociation.

Isotope Effects in the Predissociation of Excited States of N2+ Produced by Photoionization of 14N2 and 15N2 at Energies Between 24.2 and 25.6 eV