Metavalent bonding in chalcogenides: DFT-chemical pressure approach

Abstract

Understanding the chemical bond nature has attracted considerable attention as it is crucial to analyze and comprehend the different physical and chemical properties of materials. This work is considered a complementary part of our previous work in studying the nature of different types of bonding interactions in a wide variety of molecules and materials using the DFT Chemical Pressure (CP) approach. Recently, a new type of chemical bond, the metavalent bond (MVB), has been defined. We show how the CP formalism can be used to analyze and study the establishment of MVB in two chalcogenides, GeSe and PbSe, in a similar fashion as the electron localization function (ELF) profiles. This is accomplished by analyzing the CP maps of these two chalcogenides at different pressures (up to 40 GPa for GeSe and 10 GPa for PbSe). The CP maps show distinctive features related to the MVB, providing insights into the existence of such chemical interaction in the crystal structure of the two compounds. Similar to ELF profiles, CP maps can visualize and track the strength of the MVB in GeSe and PbSe under pressure.