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Photoionisation Mass-spectrometric Study of Fragmentation of SiBr4 and GeBr4 in the Range 400-1220 Angstroem

DOI: 10.1039/ft9918703717

Source and publish data:

Journal of the Chemical Society - Faraday Transactions p. 3717 - 3724 (1991)

Update date:2022-08-04

Topics:

Authors:

Creasey, Jeremy C.Creasey, Jeremy C.

Lambert, Ian R.Lambert, Ian R.

Tuckett, Richard P.Tuckett, Richard P.

Codling, KeithCodling, Keith

Frasinski, Leszek J.Frasinski, Leszek J.

et al.et al.

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Article abstract of DOI:10.1039/ft9918703717

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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