Multicoincidence mass spectrometry applied to hexamethyldisilane excited around the silicon 2p edge

Photoelectron-photoion-photoion coincidence (PEPIPICO) mass spectrometry is applied to Si 2p core ionization. The ion yield spectrum is compared to the spectrum of the tetramethylsilane molecule in order to point out resonances due to the Si-Si chemical bond. Simple coincidence mass spectra are dominated by the SiC 3 H 9 + fragment ion and do not show a strong dependence on photon wavelength. PEPIPICO spectra demonstrate that dissociation dynamics is dominated by stepwise fragmentation of SiC 3 H 9 + and that double ionization always involves Si-Si chemical bond rupture, shown to be faster than the Si-C rupture