High-resolution Si L-23-edge x-ray absorption near-edge structure (XANES) total electron yield (TEY) spectrum and photon stimulated ion desorption (PSID) spectra of condensed Si(CH3)(2)Cl-2 have been measured in the energy range of 102-115 eV using synchrotron radiation. Excitation from Si 2p to a Si-C antibonding orbital enhances the CH3+ formation, while excitation to the Si-Cl antibonding orbital gives rise to a pronounced Cl+ production. This indicates that the character of the bound terminating orbital has a significant influence on the fragmentation processes. The selective enhancement of H+ yield at a peak of similar to 106.0 eV is interpreted in terms of the excited electron in the bound orbital with strong C-H antibonding character. Applying resonant photoemission spectroscopy, the spectator Auger process was found to be the dominant decay channel for the resonantly excited Si(2p) core hole of condensed Si(CH3)(2)Cl-2. The close resemblance of the TEY and PSID spectra of solid Si(CH3)(2)Cl-2 was attributable to spectator Auger decay of core excited states and subsequent Coulomb repulsion of multivalence hole final states as proposed by the Knotek and Fiebelman mechanism.