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Bimodal internal energy distribution as a consequence ofCul-de-sac isomerization reactions

1992; Wiley; Volume: 27; Issue: 4 Linguagem: Inglês

10.1002/oms.1210270405

2376-3884

Steen Hammerum, Tore Vulpius, Henri‐Edouard Audier,

CO2 Reduction Techniques and Catalysts

Organic Mass SpectrometryVolume 27, Issue 4 p. 369-376 Account Bimodal internal energy distribution as a consequence of Cul-de-sac isomerization reactions† Steen Hammerum, Steen Hammerum Department of Chemistry, University of Copenhagen, H C. ørsted Institute, DK-2100 Copenhagen, DenmarkSearch for more papers by this authorTore Vulpius, Tore Vulpius Department of Chemistry, University of Copenhagen, H C. ørsted Institute, DK-2100 Copenhagen, DenmarkSearch for more papers by this authorHenri-Edouard Audier, Henri-Edouard Audier Ecole Polytechnique, F-91128 Palaiseau, FranceSearch for more papers by this author Steen Hammerum, Steen Hammerum Department of Chemistry, University of Copenhagen, H C. ørsted Institute, DK-2100 Copenhagen, DenmarkSearch for more papers by this authorTore Vulpius, Tore Vulpius Department of Chemistry, University of Copenhagen, H C. ørsted Institute, DK-2100 Copenhagen, DenmarkSearch for more papers by this authorHenri-Edouard Audier, Henri-Edouard Audier Ecole Polytechnique, F-91128 Palaiseau, FranceSearch for more papers by this author First published: April 1992 https://doi.org/10.1002/oms.1210270405Citations: 8 † Dedicated to Professor Dr H.-Fr. Grützmacher on the occasion of his 60th birthday. AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Abstract A simple model is developed to examine the internal energy distribution for metastable ions and the probability of reaction in the field-free regions of sector mass spectrometers in systems where the reactant ions in the ion source react by dissociation in competition with reversible isomerization to non-dissociating species. The internal energy distribution for the reacting ions is strongly dependent on whether dissociation is preceded by isomerization and back-isomerization, and it is shown that a range of reasonable combinations of rate constants for the forward and reverse isomerization result in a bimodal distribution of the internal energy for the ions that dissociate in the field-free regions. The isomerization effectively provides a kinetic reservoir of higher energy reactant ions. The reaction probability of the metastable ions varies strongly with internal energy, and the back-isomerized ions may in some instances be responsible for most of the reactions observed. A bimodal energy distribution will give rise to composite metastable peaks even though neither non-statistical behavior nor multiple reaction channels are involved. References 1 K. Levsen, Fundamental Aspects of Organic Mass Spectrometry., Verlag Chemie, Weinheim (1978). Google Scholar 2 P. J. Derrick and K. F. Donchi, Compr. Chem. 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