Evidence for Long-lived Excited States of CnH22+ Carbodications
Journal of Mass Spectrometry
The energetics, structures, stabilities and reactivities of[CnH2]2+ ions have been investigated using computational methods and experimental mass spectrometric techniques. Spontaneous decompositions of [CnH2]2+ into [CnH]+ + H+ products, observed for ions with odd-n values, have been explained by invoking the formation of excited triplet states. Even-n [CnH]+ ions possess triplet ground states with low-lying excited states, whereas odd-n ions have triplet states with energies several eV above ground singlet states. Radiationless transitions of vibrationally excited long-lived triplet state ions into singlet state continua are suggested as possible mechanisms for spontaneous deprotonation processes of odd-n [CnH2]2+ ions. Evidence for these long-lived excited states has been obtained in bimolecular single electron transfer reactions.
Appling, J.R.; Shields, George C.; and Moran, T.F.. "Evidence for Long-lived Excited States of CnH22+ Carbodications." Journal of Mass Spectrometry 21, no. 2 (1986) : 69-75.
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