Projection of excited orbitals into kinetic energies of emitted electrons in resonant Si KLL Auger decays of SiF4

Spectator resonant Auger-electron spectra have been measured in the Si 1s photoexcitation region of SiF4 using an electron spectroscopic technique combined with undulator radiation. A transition with the highest intensity in the total ion yield spectrum, which comes from excitation of a 1s electron into the 6t2 valence orbital, generates resonant Auger decays in which the excited electron remains predominantly in the valence orbital or is partly shaken up into a high-lying Rydberg orbital. The higher-lying peak generated through excitation into Rydberg orbitals induces resonant Auger decays in which the excited Rydberg electron is partly shaken up to a higher-lying Rydberg orbital or shaken down to a lower-lying valence molecular orbital. These findings exhibit a clear disentanglement effect among excited orbitals which are smeared out in the 1s electron excitation spectrum.