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Charge transfer from neutral perfluorocarbons to various cations: long-range versus short-range reaction mechanisms

Jarvis, G. K. and Kennedy, R. A. and Mayhew, C. A. and Tuckett, R. P. (2000) Charge transfer from neutral perfluorocarbons to various cations: long-range versus short-range reaction mechanisms. International Journal of Mass Spectrometry, 202 (1-3). pp. 323-343. ISSN 1387-3806

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URL of Published Version: http://dx.doi.org/10.1016/S1387-3806(00)00257-8

Identification Number/DOI: doi:10.1016/S1387-3806(00)00257-8

The bimolecular reactions of the high recombination energy cations Ar\(^+\), F\(^+\) and Ne\(^+\) with four fully saturated (CF\(_4\), C\(_2\)F\(_6\), C\(_3\)F\(_8\) and n-C\(_4\)F\(_{10}\)) and three unsaturated (C\(_2\)F\(_4\), C\(_3\)F\(_6\) and 2-C\(_4\)F\(_8\)) perfluorocarbons (PFCs) are reported. The cation branching ratios obtained from these reactions, and from the reactions with O\(_2^+\), H\(_2\)O\(^+\), N\(_2\)O\(^+\), O\(^+\), CO\(_2^+\), CO\(^+\), N\(^+\) and N\(_2^+\) (reported by us, Jarvis et al. J. Phys. Chem. 100 (1996) 17166), are compared with those determined from the threshold photoelectron-photoion coincidence spectra of the PFCs at the recombination energies of the reagent cations. This comparison provides information that helps to interpret the dynamics of charge-transfer, and whether it occurs via a long-range or a short-range mechanism. Energy resonance and good Franck-Condon factors connecting the ground electronic state of a reactant neutral molecule to one of its ionic states, at the recombination of the reagent cation, are generally considered to be sufficient for long-range charge-transfer to occur. However, the results from this study imply that good Franck-Condon factors are not critical in determining the efficiency of a long-range charge-transfer. Instead, the results suggest that, in addition to the requirement for energy resonance, the electron taking part in the charge-transfer process must be removed from a molecular orbital which is unshielded from the approaching reagent cation. This enables the cation to exert an influence on the electron at large impact parameters.

Type of Work:Article
Date:2000 (Publication)
School/Faculty:Schools (1998 to 2008) > School of Chemical Sciences
Department:School of Chemistry, School of Physics
Keywords:SIFT; Charge transfer; Perfluorocarbons; TPEPICO
Subjects:QD Chemistry
QC Physics
Institution:University of Birmingham
Copyright Holders:Elsevier B.V.
ID Code:729
Refereed:YES
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