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

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

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Thiophenes
Acetylene
Pyrroles
Photoelectrons
Spectroscopy
Ions
Electron transitions
Electron energy levels
Decomposition

Keywords

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

Cite this

Rennie, Emma E. ; Cooper, Louise ; Shpinkova, Larisa G. ; Holland, D. M P ; Shaw, David A. ; Mayer, Paul M. / Threshold photoelectron photoion coincidence spectroscopy sheds light on the dissociation of pyrrole and thiophene molecular ions. In: International Journal of Mass Spectrometry. 2010 ; Vol. 290, No. 2-3. pp. 142-144.
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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. {\circledC} 2009 Elsevier B.V. All rights reserved.",
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Threshold photoelectron photoion coincidence spectroscopy sheds light on the dissociation of pyrrole and thiophene molecular ions. / Rennie, Emma E.; Cooper, Louise; Shpinkova, Larisa G.; Holland, D. M P; Shaw, David A.; Mayer, Paul M.

In: International Journal of Mass Spectrometry, Vol. 290, No. 2-3, 15.02.2010, p. 142-144.

Research output: Contribution to journalArticle

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T1 - Threshold photoelectron photoion coincidence spectroscopy sheds light on the dissociation of pyrrole and thiophene molecular ions

AU - Rennie, Emma E.

AU - Cooper, Louise

AU - Shpinkova, Larisa G.

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AU - Shaw, David A.

AU - Mayer, Paul M.

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