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Competition of Proton and Electron Transfers in Gas‐Phase Reactions of Hydrogen‐Containing Dications CHX 2+ (X=F, Cl, Br, I) with Atoms, Nonpolar and Polar Molecules
Author(s) -
Roithová Jana,
Herman Zdenek,
Schröder Detlef,
Schwarz Helmut
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200500888
Subject(s) - chemistry , molecule , proton , electron transfer , chemical polarity , triatomic molecule , ion , proton coupled electron transfer , polar , hydrogen , electron , photochemistry , organic chemistry , physics , quantum mechanics , astronomy
Abstract The competition between proton and electron transfer in reactions of mass‐selected dications CHX 2+ (X=F, Cl, Br, and I) with rare gas atoms (Ne, Ar, Kr, and Xe) and selected molecular reagents (N 2 , O 2 , CO, H 2 O, and HCl) is studied in the gas phase. In the ion–molecule reactions of CHX 2+ dications with atoms and nonpolar molecules, it is the energy balance of electron transfer that acts as the decisive factor: when the exothermicity of electron transfer exceeds 2 eV, this process predominates at the expense of bond‐forming proton transfer. In marked contrast, the reactions between these triatomic dications and polar molecules are governed for the benefit of the thermochemically more favored products resulting from proton transfer.