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

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry
Andrés GuerreroDieter Lenoir

Abstract

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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Citations

Dec 8, 2015·Nature Nanotechnology·Karthik Thimmavajjula NarasimhaNicholas A Melosh
Feb 23, 2012·Chemistry : a European Journal·José-Luis M AbboudEva Roos Nerut
Apr 29, 2015·Journal of the American Chemical Society·Tatyana S ZhukAndrey A Fokin

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