Long-Range Forces in Rock-Salt-Type Tellurides and How they Mirror the Underlying Chemical Bonding.

Abstract

Chemical bonding in main-group IV chalcogenides is an intensely discussed topic, easily understandable because of their remarkable physical properties that predestine these solid-state materials for their widespread use in, for instance, thermoelectrics and phase-change memory applications. The atomistic origin of their unusual property portfolio remains somewhat unclear, however, even though different and sometimes conflicting chemical-bonding concepts have been introduced in the recent years. Here, it is proposed that projecting phononic force-constant tensors for pairs of atoms along differing directions and ranges provide a suitable and quantitative descriptor of the bonding nature for these materials. In combination with orbital-based quantitative measures of covalency such as crystal orbital Hamilton populations (COHP), it is concluded that the well-established many-center and even n-center bonding is an appropriate picture of the underlying quantum-chemical bonding mechanism, supporting the recent proposal of hyperbonded phase-change materials.