State-specific photochemistry for SiCl4 adsorbed on Si(100) at ∼90 K following the Cl 2p and Si 2p core-level excitations has been investigated by photon-stimulated ion desorption, resonant photoemission, ion energy distribution, and soft x-ray absorption spectral measurements. The Cl+ photon-stimulated ion desorption spectrum and Cl L-edge x-ray absorption spectrum for condensed SiCl4 exhibit a clear dissimilarity unlike the other fragments, viz. SiCl3+, SiCl2+, SiCl+, and Si+. The Cl+ desorption yield shows a significant enhancement following the Cl 2p→8a1* excitation, while the Si 2p→8a1* excitation leads to the scarce enhancement of the Cl+ yield. The Cl+ ion energy distributions via the Cl 2p→8a1* excitation are shifted to higher energy (0.3–0.4 eV) compared to those via the Cl 2p→9t2* and Si 2p→8a1* excitations. The enhancement of the Cl+ desorption yield at the Cl(2p)−18a1* resonance is attributed to the higher ion escape energy. These results provide an insight into the comprehensive understanding of the state-selective fragmentation of molecules via core-level excitation.
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