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Bioelectrochemistry.. Ions, Surfaces, Membranes by Blank M. (ed.)

By Blank M. (ed.)

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F- ions produced via high-lying Rydberg states would be dominant at higher energy, and hence responsible for features 2-11 in the ion yield. If this is true, it negates the generally accepted rule that it is low-n, and not high-n, Rydberg states which interact most strongly with ion-pair states. However, most of the ion-pair experiments on polyatomics to date have studied halogenated molecules where the lowest ion-pair threshold lies below the first ionisation energy [34], so by definition it is the low-n states which have been the most widely studied.

Finally, it is noted that shape resonances have been observed in the yields of many anions in both SF6 and CF4 above 25 eV [23, 29]. There is no obvious evidence for such peaks in our ion yields from SF5CF3, but it would be surprising if they were not present. 5 Conclusions The peaks in the F- yields from both SF6 and CF4 have been assigned to Rydberg transitions [21, 22], and the assignments are not repeated here. However, there is some disagreement whether the transitions observed in the VUV absorption spectrum of SF5CF3 [7, 20], and indeed the CF*3 fluorescence excitation spectrum [36], are due to intravalence or Rydberg transitions.

1. The small rise in signal at 12 eV seen in the F- ion yields from CF3Cl and CF3Br is considered to result from second-order radiation, and is exaggerated by normalisation to photon flux which is low at this energy. In all three cases the F- signal shows a linear rise with gas pressure, indicating that F- ions are formed by unimolecular ion-pair dissociation. 0 –j –i –j –j –j –j 9 9 9 9 10-4 10-5 10-7 10-7 9 10-6 9 10-6 9 10-4 9 9 9 9 9 10-6 10-6 10-6 10-6 10-6 a Adiabatic IE for CF3Cl [10], CF3Br [10], and CF3I [21] are given in parentheses Observed AE from this work.

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