Discovering electron transfer driven changes in chemical bonding in lead chalcogenides (PbX, where X = Te, Se, S, O)

Abstract: Understanding the nature of chemical bonding in solids is crucial to comprehend the physical and chemical properties of a given compound. To explore changes in chemical bonding in lead chalcogenides (PbX, where X = Te, Se, S, O), a combination of property-, bond breaking- and quantum-mechanical bonding descriptors have been applied. The outcome of our explorations reveals an electron transfer driven transition from metavalent bonding in PbX (X = Te, Se, S) to iono-covalent bonding in beta-PbO. Metavalent bonding is characterized by adjacent atoms being held together by sharing about a single electron and small electron transfer (ET). The transition from metavalent to iono-covalent bonding manifests itself in clear changes in these quantum-mechanical descriptors (ES and ET), as well as in property-based descriptors (i.e. Born effective charge, dielectric function, effective coordination number (ECON) and mode-specific Grueneisen parameter, and in bond breaking descriptors (PME). Metavalent bonding collapses, if significant charge localization occurs at the ion cores (ET) and/or in the interatomic region (ES). Predominantly changing the degree of electron transfer opens possibilities to tailor materials properties such as the chemical bond and electronic polarizability, optical band gap and optical interband transitions characterized by the imaginary part of the dielectric function. Hence, the insights gained from this study highlight the technological relevance of the concept of metavalent bonding and its potential for materials design.