Abstract
Discrete and shape resonances observed in photoabsorption spectra of molecules near core ionization edges are described using the SiH4, (silane) and SiF4, (Silicon tetrafluoride) molecules excited near the Sils and Si2p edges as model systems. We illustrate the molecular specificity of such resonances by comparison of SiH4, and the isoelectronic argon atom. Then we analyze the effect of the strength of the molecular field by a further comparison with SiF4.
Electronic relaxation processes of such resonances identified primarily by photoelectron spectroscopy in SiH4, and SiF4, excited near the Si2p edge are presented and described in terms of autoionization and Auger effect. Competition with a primary fast dissociation process in SiH4, is invoked.
Dissociation of the residual ions after a Si2p excitation of SiF4, is evidenced with mass spectrometry in the normal and photoion-photoion coïncidence modes. Multiple Auger are found to be other electronic decay channels. Limitations of the site selectivity of core excitation among final dissociation products in molecules are briefly discussed.
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Nenner, I. (1987). Inner Shell Resonances in Molecular Photoionization. In: Connerade, J.P., Esteva, J.M., Karnatak, R.C. (eds) Giant Resonances in Atoms, Molecules, and Solids. NATO ASI Series, vol 151. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-2004-1_16
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