Evidence for Long-lived Excited States of CnH22+ Carbodications

Authors

J.R. Appling
George C. Shields, Bucknell UniversityFollow
T.F. Moran

Publication Date

1986

Description

The energetics, structures, stabilities and reactivities of[C_nH₂]²⁺ ions have been investigated using computational methods and experimental mass spectrometric techniques. Spontaneous decompositions of [C_nH₂]²⁺ into [C_nH]⁺ + H⁺ products, observed for ions with odd-n values, have been explained by invoking the formation of excited triplet states. Even-n [C_nH]⁺ 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 [C_nH₂]²⁺ ions. Evidence for these long-lived excited states has been obtained in bimolecular single electron transfer reactions.

Journal

Journal of Mass Spectrometry

Volume

21

Issue

2

First Page

69

Last Page

75

Department

Chemistry

Link to Published Version

http://onlinelibrary.wiley.com/doi/10.1002/oms.1210210205/abstract

Recommended Citation

Appling, J.R.; Shields, George C.; and Moran, T.F.. "Evidence for Long-lived Excited States of CnH22+ Carbodications." Journal of Mass Spectrometry (1986) : 69-75.