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  • The production of C7Hn2+ (with n=6, 8) dications from 2,5-norbornadiene (NBD) and their reactivity toward Xe and N-2 are studied using multipole-based tandem mass spectrometry techniques coupled with ionization either by collisions with energetic electrons or with tunable VUV photons coming from the SOLEIL synchrotron facility. From the photoionization studies, an apparent double photoionization energy of (2)AE(NBD) = (22.80 +/- 0.08) eV is derived, while the appearance energy of the C7H62+ fragment is only slightly higher at (23.08 +/- 0.10) eV and the hydrogen-depleted dication dominates the mass spectrum at photon energies above about 24 eV. Theoretical calculations predict the adiabatic (IE)-I-2(NBD) as about 1.26 eV lower than the experimental value, which is attributed to the occurrence of significant Franck-Condon effects. Concerning the formation of C7H62+, theory and experiment indicate that the dehydrogenation product corresponds to the cycloheptatrienylidene dication, as is formed upon dissociative double ionization of previously studied C7H8 isomers (namely toluene and cycloheptatriene, CHT). The C7H62+ formation results from the overall exothermic rearrangement of NBD2+ into CHT2+ and thus only little extra energy is required to afford dehydrogenation. Further, the NBD2+/CHT2+ isomerization affects the reactivity of C7H82+ and C7H62+ dications toward Xe and N-2, leading to the formation of the dications C7H6Xe2+ and C7H6N22+, respectively. The high efficiency of formation of the diazo dication C7H6N22+ suggests that reactions of organic dications with N-2 may play an important role in the chemistry of nitrogen and hydrocarbon-rich atmospheres of planets and moons.
  • The production of C7Hn2+ (with n=6, 8) dications from 2,5-norbornadiene (NBD) and their reactivity toward Xe and N-2 are studied using multipole-based tandem mass spectrometry techniques coupled with ionization either by collisions with energetic electrons or with tunable VUV photons coming from the SOLEIL synchrotron facility. From the photoionization studies, an apparent double photoionization energy of (2)AE(NBD) = (22.80 +/- 0.08) eV is derived, while the appearance energy of the C7H62+ fragment is only slightly higher at (23.08 +/- 0.10) eV and the hydrogen-depleted dication dominates the mass spectrum at photon energies above about 24 eV. Theoretical calculations predict the adiabatic (IE)-I-2(NBD) as about 1.26 eV lower than the experimental value, which is attributed to the occurrence of significant Franck-Condon effects. Concerning the formation of C7H62+, theory and experiment indicate that the dehydrogenation product corresponds to the cycloheptatrienylidene dication, as is formed upon dissociative double ionization of previously studied C7H8 isomers (namely toluene and cycloheptatriene, CHT). The C7H62+ formation results from the overall exothermic rearrangement of NBD2+ into CHT2+ and thus only little extra energy is required to afford dehydrogenation. Further, the NBD2+/CHT2+ isomerization affects the reactivity of C7H82+ and C7H62+ dications toward Xe and N-2, leading to the formation of the dications C7H6Xe2+ and C7H6N22+, respectively. The high efficiency of formation of the diazo dication C7H6N22+ suggests that reactions of organic dications with N-2 may play an important role in the chemistry of nitrogen and hydrocarbon-rich atmospheres of planets and moons. (en)
Title
  • Reactivity and properties of dications generated by photoionization of 2,5-norbornadiene
  • Reactivity and properties of dications generated by photoionization of 2,5-norbornadiene (en)
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  • Reactivity and properties of dications generated by photoionization of 2,5-norbornadiene
  • Reactivity and properties of dications generated by photoionization of 2,5-norbornadiene (en)
skos:notation
  • RIV/00216208:11310/13:10159274!RIV14-GA0-11310___
http://linked.open...avai/predkladatel
http://linked.open...avai/riv/aktivita
http://linked.open...avai/riv/aktivity
  • I, P(GA203/09/1223), P(GAP208/11/0446), Z(MSM0021620857)
http://linked.open...iv/cisloPeriodika
  • Feb 15
http://linked.open...vai/riv/dodaniDat
http://linked.open...aciTvurceVysledku
http://linked.open.../riv/druhVysledku
http://linked.open...iv/duvernostUdaju
http://linked.open...titaPredkladatele
http://linked.open...dnocenehoVysledku
  • 101554
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  • RIV/00216208:11310/13:10159274
http://linked.open...riv/jazykVysledku
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  • xenon; synchrotron radiation; reactive monitoring; photoionization; norbornadiene; dications (en)
http://linked.open.../riv/klicoveSlovo
http://linked.open...odStatuVydavatele
  • NL - Nizozemsko
http://linked.open...ontrolniKodProRIV
  • [F364064C2D08]
http://linked.open...i/riv/nazevZdroje
  • International Journal of Mass Spectrometry
http://linked.open...in/vavai/riv/obor
http://linked.open...ichTvurcuVysledku
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http://linked.open...vavai/riv/projekt
http://linked.open...UplatneniVysledku
http://linked.open...v/svazekPeriodika
  • 336
http://linked.open...iv/tvurceVysledku
  • Schröder, Detlef
  • Zins, Emilie-Laure
  • Žabka, Ján
  • Polášek, Miroslav
  • Roithová, Jana
  • Alcaraz, Christian
  • Shaffer, Christopher J.
  • Ascenzi, Daniela
http://linked.open...ain/vavai/riv/wos
  • 000316713700002
http://linked.open...n/vavai/riv/zamer
issn
  • 1387-3806
number of pages
http://bibframe.org/vocab/doi
  • 10.1016/j.ijms.2012.12.002
http://localhost/t...ganizacniJednotka
  • 11310
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