Relaxation processes following excitation and ionization of SiF4 in the vicinity of the silicon 2p threshold. II. Dissociation of the molecular ions

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Abstract
Partial ion yields from photoionization of SiF4 have been measured with time‐of‐flight mass spectrometry, photoion–photoion coincidence and triple photoion coincidence techniques using synchrotron radiation from 100 to 136 eV, in the region of the silicon 2p edge where strong resonances are found. From the photon energy dependence of positive ion pairs and of doubly charged fragment intensities, with a suitable normalization procedure, we have estimated the total double photoionization cross section. Below the Si2p edge, the double to single dissociative ionization branching ratio follows the resonance behavior, and is consistent with the photoelectron results of de Souza et al. (Paper I) and discussed in terms of multibond breaking dissociation pathways of residual excited ions (singly and doubly charged) produced by resonant Auger decay processes. Above the Si2p edge, the fragmentation is found to originate from dissociative double ionization occurring after normal Auger processes. The small additional contribution of triple dissociative ionization is consistent with a second order Auger process. In contrast, the underlying valence ionization continuum is responsible for all parent intensity and most of the SiF+3 fragment expected from the normal dissociative ionization channels. The measurement of appearance energies of fragment ion pairs by the photoion–photoion coincidence method, offers a direct measurement of the first direct double ionization onset in SiF4 and new values for other dissociative SiF2+4 states which complement those found by Auger spectroscopy.