Comparison of electronic decay of valence ionized fluorinated carbanions and their acids

Mu¨ller, I. B.; Zobeley, J.; Cederbaum, L. S.
July 2002
Journal of Chemical Physics;7/15/2002, Vol. 117 Issue 3, p1085
Academic Journal
The ionization and double-ionization spectra of fluorinated carbanions of various chain lengths are compared with those of their corresponding acids. For the acidic systems we find a dramatic relative shift of the double-ionization spectra to higher energies due to the presence of just one additional proton. The impact of the proton on the ionization spectra is also important, but results in only half of the double-ionization spectra's shift. A molecular electronic decay mechanism is found to be operative in the valence region of the molecules under investigation. The impact of this decay is more substantial for the anions. The threshold for electronic decay (i.e., the first double-ionization potential) is at much lower energy for the anions than for the acids. Interestingly, the localization pattern of the holes in the decay channels is, in contrast to the decay threshold, only a little affected by protonation. We also compare the impact of electron correlation effects on the ionization and double-ionization spectra of the series of fluorinated carbanions and of their acids.


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