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Open Access Green as soon as Postprint is submitted to ZB.
Single-electron self-exchange between cage hydrocarbons and their radical cations in the gas phase.
ChemPhysChem 11, 713-721 (2010)
We show that the radical cations of adamantane (C(10)H(16)(*+), 1H(*+)) and perdeuteroadamantane (C(10)D(16)(*+), 1D(*+)) are stable species in the gas phase. The radical cation of adamantylideneadamantane (C(20)H(28)(*+), 2H(*+)) is also stable (as in solution). By using the natural (13)C abundances of the ions, we determine the rate constants for the reversible isergonic single-electron transfer (SET) processes involving the dyads 1H(*+)/1H, 1D(*+)/1D and 2H(*+)/2H. Rate constants for the reaction 1H(*+)+1D <==> 1H+1D(*+) are also determined and Marcus' cross-term equation is shown to hold in this case. The rate constants for the isergonic processes are extremely high, practically collision-controlled. Ab initio computations of the electronic coupling (H(DA)) and the reorganization energy (lambda) allow rationalization of the mechanism of the process and give insights into the possible role of intermediate complexes in the reaction mechanism.
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Publication type
Article: Journal article
Document type
Scientific Article
Keywords
Ab initio calculations; Cage compounds; Electron transfer; Hydrocarbons; Radical ions
ISSN (print) / ISBN
1439-4235
e-ISSN
1439-7641
Journal
ChemPhysChem
Quellenangaben
Volume: 11,
Issue: 3,
Pages: 713-721
Publisher
Wiley
Publishing Place
Weinheim
Non-patent literature
Publications
Reviewing status
Peer reviewed
Institute(s)
Institute of Ecological Chemistry (IOEC)