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Guerrero, A.* ; Herrero, R.* ; Quintanilla, E.* ; Davalos, J. Z.* ; Abboud, J.L.M.* ; Coto, P.B.* ; Lenoir, D.

Single-electron self-exchange between cage hydrocarbons and their radical cations in the gas phase.

ChemPhysChem 11, 713-721 (2010)
DOI
Open Access Green möglich sobald Postprint bei der ZB eingereicht worden ist.
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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Publikationstyp Artikel: Journalartikel
Dokumenttyp Wissenschaftlicher Artikel
Korrespondenzautor
Schlagwörter Ab initio calculations; Cage compounds; Electron transfer; Hydrocarbons; Radical ions
ISSN (print) / ISBN 1439-4235
e-ISSN 1439-7641
Zeitschrift ChemPhysChem
Quellenangaben Band: 11, Heft: 3, Seiten: 713-721 Artikelnummer: , Supplement: ,
Verlag Wiley
Verlagsort Weinheim
Nichtpatentliteratur Publikationen
Begutachtungsstatus Peer reviewed
Institut(e) Institute of Ecological Chemistry (IOEC)