Journal of the Chemical Society - Faraday Transactions p. 3717 - 3724 (1991)
Update date:2022-08-04
Topics:
Creasey, Jeremy C.
Lambert, Ian R.
Tuckett, Richard P.
Codling, Keith
Frasinski, Leszek J.
et al.
The non-radiative decay channels of the valence electronic states of SiBr4+ and GeBr4+ have been studied in the range 1220-400 Angstroem (10-31 eV) by photoionisation mass spectrometry.Ion-yield curves for the parent ions and for MBr3+, MBr2+, MBr+, M+ and Br+ (M = Si, Ge) have been obtained, as well as the relative photoionisation branching rations.The appearance thresholds for SiBr3+ and GeBr3+ occur at 11.31 and 10.97 eV, respectively.They lie within the Franck-Condon region of the ground state of SiBr4+ and GeBr4+, and are at the thermodynamic thresholds for SiBr3+ + Br and GeBr3+ + Br.The smaller fragment ions have appearance thresholds which relate to energies for excited electronic states of SiBr4+ and GeBr4+, and not to the lower-lying thermodynamic energy of the fragment ion.The results are discussed with reference to our earlier work on radiative decay from excited states of SiBr4+ and GeBr4+ (J.Chem.Soc.Faraday Trans., 1990, 86, 2021).We have obtained a new value for the ionisation potential of SiBr3 of 7.6 +/- 0.4 eV, and we suggest that the previously accepted value for SiBr2 (12 +/- 1 eV) is ca. 3.5 eV too high.
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