Production of excited neutral and ionic photofragments following core-level excitation in molecules

Abstract

We have performed the first experiments to examine the neutral fragmentation paths following direct core-level excitation in a molecule. Using monochromatized synchrotron radiation in the range 100–140 eV, we have monitored the dispersed UV/optical fluorescence resulting from excitation of a Si 2p electron in SiF4. The main features in the fluorescence spectrum have been identified as emission from the SiF+4 D state and from excited SiF, Si, F, and Si+. Features in the fluorescence excitation spectra are assigned to excitation of a Si 2p electron to unoccupied valence orbitals, Rydberg orbitals, and shape resonances. There is a large enhancement in the yield of excited-state fragments following core-to-Rydberg excitation, which is due to the greater probability of the core-excited Rydberg state decaying, via a resonant Auger process, to highly excited, unbound states of SiF+4.