A new method to study complex materials in solid state chemistry: application to chalcogenide materials

We show that a combined application of Mössbauer spectroscopy and other experimental tools such as X‐ray photoelectron spectroscopy, X‐ray absorption spectroscopy and nuclear magnetic resonance provides a coherent picture of the local electronic structure in chalcogenide materials. In order to develop this idea we propose an analysis of the Sn, Sb and Te local electronic structures for three different systems of materials. The first example concerns the In–Sn–S system. We show that Li insertion in In₁₆Sn₄S₃₂ leads to changes of the Sn oxidation states from Sn(IV) to Sn(II). The second example concerns materials of the Tl–Sb–S system. We show that variations of the ¹²¹Sb Mössbauer isomer shift and surface of the first peak of the X‐ray absorption spectra at the Sb L_III edge can be linearly correlated because of the main influence of the Sb 5s electrons. This is explained by changes in the local environment of the Sb atoms. The last example concerns the crystalline phases of the Tl–Sn–Te system. The formal oxidation numbers of the Te atoms are determined from ¹²⁵Te Mössbauer spectroscopy and X‐ray photoelectron spectroscopy. They are related to the different types of bonds involving the Te atoms in the Tl–Sn–Te compounds.