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Rearrangement and fragmentation pathways of [C3H7Z]+ions (Z = NH and S): are ion–neutral complexes important?11 Dedicated to Professor Jim Morrison on the occasion of his 75th birthday.

Authors
Journal
International Journal of Mass Spectrometry
1387-3806
Publisher
Elsevier
Publication Date
Volume
194
Identifiers
DOI: 10.1016/s1387-3806(99)00127-x
Keywords
  • [C3H8N]+
  • [C3H7S]+
  • Metastable Ion
  • G2
  • Rrkm
  • Ion–Neutral Complex
  • Heat Of Formation
Disciplines
  • Chemistry

Abstract

Abstract High level ab initio calculations at the G2(ZPE = MP2) level have been used to characterize the potential energy surfaces for rearrangement/fragmentation of various [C 3H 8N] + and [C 3H 7S] + isomers. In contrast to the behavior in the corresponding [C 3H 7O] + system, it is found that ion–neutral complexes are only of minor importance in determining the fragmentation characteristics. Either dissociation of such complexes occurs too fast due to a large barrier to their formation ([C 3H 8N] + system), or alternative lower-energy rearrangement routes that do not involve ion–neutral complexes are available ([C 3H 7S] + system). Calculated thermochemical quantities such as heats of formation and reaction barriers are found to be in reasonable agreement with experimental results. Metastable ion product abundances and results of both deuterium- and 13C-labeling experiments are rationalized in terms of the calculated potential energy surfaces and rate constants obtained using Rice-Ramsperger-Kassel-Marcus theory.

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