Threshold photoelectron photoion coincidence spectroscopy sheds light on the dissociation of pyrrole and thiophene molecular ions

Emma E. Rennie, Louise Cooper, Larisa G. Shpinkova, D. M P Holland, David A. Shaw, Paul M. Mayer

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Threshold photoelectron photoion coincidence spectroscopy was employed to examine the loss of ethyne from ionized pyrrole and thiophene near their dissociation thresholds as a function of internal energy and reaction time. The B3-LYP/6-311+G(3df,3pd) minimum energy reaction pathways for ethyne loss from both ions are presented. The experimental molecular ion breakdown curves were modeled with RRKM theory. For ionized pyrrole, the fitting results in confirmation of the transition state energies in the decomposition pathways. For ionized thiophene, the modeling suggests that ethyne loss is a concerted process rather than a true step-wise reaction. If so, the fitting yields a ?fH298 for CH2CS+{radical dot} of 1033 ± 2 kJ mol-1. © 2009 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)142-144
Number of pages3
JournalInternational Journal of Mass Spectrometry
Volume290
Issue number2-3
DOIs
Publication statusPublished - 15 Feb 2010

Keywords

  • Activation energy and entropy
  • Density functional theory
  • Pyrrole ion
  • Thiophene ion
  • Threshold photoelectron photoion coincidence spectroscopy

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