Relaxation processes following excitation and ionization of SiF4 in the vicinity of the silicon 2p threshold. I. Electronic relaxation processes

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Abstract
The photoelectron and Auger spectra of SiF4 have been measured, using synchrotron radiation in the 100 to 125 eV photon energy range in the vicinity of the Si2p ionization threshold. Partial photoionization cross sections have been obtained for outer, inner valence states and satellite states in the same energy range, together with the threshold photoelectron spectrum. At the energies of the discrete resonances observed below 112 eV, the core excited molecule is found to decay mostly by resonant Auger and to a small extent by autoionization. Among the resonant Auger pathways, those in which two electrons (rather than one) are ejected are found to play a dominant role. Above threshold, especially around the energy of the first continuum resonance, normal Auger processes are observed. Also, we offer a new interpretation of the Auger spectrum based on large configuration interaction in the final state and on the screening of the Si2p hole by the lone‐pair electrons of the fluorine atoms. We also find some evidence of cascade Auger processes which explain the formation of triply ionized molecules.