Počet záznamů: 1
Reactivity and properties of dications generated by photoionization of 2,5-norbornadiene
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SYSNO ASEP 0392683 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Reactivity and properties of dications generated by photoionization of 2,5-norbornadiene Tvůrce(i) Shaffer, Christopher (UOCHB-X) RID
Schröder, Detlef (UOCHB-X)
Roithová, J. (CZ)
Zins, E. L. (FR)
Alcaraz, C. (FR)
Žabka, Ján (UFCH-W) RID, ORCID, SAI
Polášek, Miroslav (UFCH-W) RID, ORCID
Ascenzi, D. (IT)Celkový počet autorů 8 Zdroj.dok. International Journal of Mass Spectrometry. - : Elsevier - ISSN 1387-3806
Roč. 336, Feb 15 (2013), s. 17-26Poč.str. 10 s. Jazyk dok. eng - angličtina Země vyd. NL - Nizozemsko Klíč. slova dications ; norbornadiene ; photoionization ; reactive monitoring ; synchrotron radiation Vědní obor RIV CF - Fyzikální chemie a teoretická chemie CEP GA203/09/1223 GA ČR - Grantová agentura ČR GAP208/11/0446 GA ČR - Grantová agentura ČR Institucionální podpora UOCHB-X - RVO:61388963 ; UFCH-W - RVO:61388955 UT WOS 000316713700002 EID SCOPUS 84873311961 DOI 10.1016/j.ijms.2012.12.002 Anotace 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. (C) 2012 Elsevier B.V. All rights reserved. Pracoviště Ústav organické chemie a biochemie Kontakt asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Viktorie Chládková, Tel.: 232 002 434 Rok sběru 2014
Počet záznamů: 1