Probing matrix isolated SiO molecular clusters by X-ray absorption spectroscopy

TheK absorption edge of Si in matrix isolated SiO molecular clusters was studied for various dilutionsR(Ar/SiO). The spectra from the clusters at different dilutions show a dramatic evolution in their relative intensity. Two types of spectral features from Si atoms present in the clusters could be detected in the spectra. The first is due to the Si atoms which are tetrahedrally coordinated to Si and O atoms responsible for the presence of different Si oxidation states. The Si⁺, Si³⁺ and Si⁴⁺ oxidation states in SiO clusters and in bulk were readily identified. The Si²⁺ oxidation state whose abundance in SiO clusters is predicted by structural considerations is not clearly observed. The second type of feature, whose intensity decreases with the dilution R, can be attributed to the presence of Si atoms possessing unsaturated bonds. In order to explain this the clustering of 4–6 SiO molecules is simulated to yield different tetrahedral bonding microstructures in which the well coordinated as well as under coordinated Si atoms are present. The behaviour of the spectral features resulting from these microstructures is discussed.