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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 2000 (Publication) Schools (1998 to 2008) > School of Chemical Sciences School of Chemistry, School of Physics SIFT; Charge transfer; Perfluorocarbons; TPEPICO QD ChemistryQC Physics University of Birmingham Elsevier B.V. 729 YES

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