Probing the Validity of the Zintl−Klemm Concept for Alkaline-Metal Copper Tellurides by Means of Quantum-Chemical Techniques

Abstract

Understanding the nature of bonding in solid-state materials is of great interest for their designs, because the bonding nature influences the structural preferences and chemical as well as physical properties of solids. In the cases of tellurides, the distributions of valence-electrons are typically described by applying the Zintl−Klemm concept. Yet, do these Zintl−Klemm treatments provide adequate pictures that help us understanding the bonding nature in tellurides? To answer this question, we followed up with quantum-chemical examinations on the electronic structures and the bonding nature of three alkaline-metal copper tellurides, i.e., NaCu3Te2, K2Cu2Te5, and K2Cu5Te5. In doing so, we accordingly probed the validity of the Zintl−Klemm concept for these ternary tellurides, based on analyses of the respective projected crystal orbital Hamilton populations (−pCOHP) and Mulliken as well as Löwdin charges. Since all of the inspected tellurides are expected to comprise Cu−Cu interactions, we also paid particular attention to the possible presence of closed-shell interactions.