Abstract
This paper reports on the structural investigation of lithium and sodium thiosilicate crystals and glasses by means of X-ray photoelectron spectroscopy and ab initio calculation. The results are analysed in conjunction with previously reported 29Si NMR data. While NMR proved to be an effective tool for the quantitative discrimination of edge- and corner-sharing tetrahedra existing in these materials, X-ray photoelectron spectroscopy (XPS) gives information on the nature of Si-S bonds, i.e. bridging and non-bridging bonds. The main result is the noticeable difference existing between the structures of lithium and sodium thiosilicate glasses, which, according to XPS data, is due to different electronic redistributions over the network when one or the other alkali is added, the sodium addition resulting in a change in the electronic distribution over the entire network.