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Fragmentation of Energy Selected Butadiyne‐ and 1,3‐Pentadiyne Radical Cations
Author(s) -
Dannacher Josef,
Heilbronner Edgar,
Stadelmann JeanPierre,
Vogt Jürgen
Publication year - 1979
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19790620716
Subject(s) - chemistry , fragmentation (computing) , excited state , ion , isomerization , ionization , photochemistry , ionic bonding , atomic physics , electron ionization , radical ion , biochemistry , physics , organic chemistry , computer science , catalysis , operating system
Monomolecular fragmentations of butadiyne‐ and 1,3‐pentadiyne radical cations in their electronically excited states have been investigated by use of the photoelectron‐photoion coincidence technique. Breakdown curves for the molecular and various fragment ions have been recorded over the ionization energy range of 9 to 17 eV. These breakdown curves reveal the extent of the competition between the radiative relaxation (ion fluorescence) and the non‐radiative internal conversion followed by fragmentation for the decay of the first excited electronic states. Extensive hydrogen scrambling and/or ionic‐carbon‐skeleton isomerization takes place prior to fragmentation, as revealed by the breakdown curves obtained for the site specifically deuteriated 1,3‐pentadiynes.