Discovering Electron‐Transfer‐Driven Changes in Chemical Bonding in Lead Chalcogenides (PbX, where X = Te, Se, S, O)

Advanced Materials, vol. 32, pp. e2005533

Abstract

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 are applied. The outcome of the explorations reveals an electron‐transfer‐driven transition from metavalent bonding in PbX (X = Te, Se, S) to iono‐covalent bonding in β‐PbO. Metavalent bonding is characterized by adjacent atoms being held together by sharing about a single electron (ES ≈ 1) 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 (Z*), dielectric function ε(ω), effective coordination number (ECoN), and mode‐specific Grüneisen parameter (γTO)), and in bond‐breaking descriptors. 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 material properties such as the chemical bond (Z*) and electronic (ε∞) polarizability, optical bandgap, and optical interband transitions characterized by ε2(ω). Hence, the insights gained from this study highlight the technological relevance of the concept of metavalent bonding and its potential for materials design.

Authors 11

1. Stefan Maier Aachen Institute of Physics IA

   RWTH Aachen University

   Affiliation as printed

   Institute of Physics IA RWTH Aachen University Aachen 52074 Germany

   Institute of Physics IA, RWTH Aachen University, Aachen, 52074 Germany

2. Simon Steinberg Aachen Institute of Inorganic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Inorganic Chemistry RWTH Aachen University Aachen 52056 Germany

   Institute of Inorganic Chemistry, RWTH Aachen University, Aachen, 52056 Germany

3. Yudong Cheng Aachen Institute of Physics IA

   RWTH Aachen University

   Affiliation as printed

   Institute of Physics IA RWTH Aachen University Aachen 52074 Germany

   Institute of Physics IA, RWTH Aachen University, Aachen, 52074 Germany

4. Carl‐Friedrich Schön Aachen Institute of Physics IA

   RWTH Aachen University

   Affiliation as printed

   Institute of Physics IA RWTH Aachen University Aachen 52074 Germany

   Institute of Physics IA, RWTH Aachen University, Aachen, 52074 Germany

5. Mathias Schumacher Aachen Institute for Theoretical Solid State Physics

   RWTH Aachen University

   Affiliation as printed

   Institute for Theoretical Solid State Physics RWTH Aachen University Aachen 52056 Germany

   Institute for Theoretical Solid State Physics, RWTH Aachen University, Aachen, 52056 Germany

6. Riccardo Mazzarello Aachen Institute for Theoretical Solid State Physics

   Jülich Aachen Research Alliance · RWTH Aachen University

   Affiliation as printed

   Institute for Theoretical Solid State Physics RWTH Aachen University Aachen 52056 Germany

   Jülich‐Aachen Research Alliance (JARA‐HPC) RWTH Aachen University Aachen 52056 Germany

   Institute for Theoretical Solid State Physics, RWTH Aachen University, Aachen, 52056 Germany

7. Pavlo Golub

   Czech Academy of Sciences, Heyrovsky Institute

   Affiliation as printed

   J. Heyrovsky Institute of Physical Chemistry Department of Theoretical Chemistry Dolejškova 2155/3 Prague 8 182 23 Czech Republic

8. Ryky Nelson Aachen Institute of Inorganic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Inorganic Chemistry RWTH Aachen University Aachen 52056 Germany

   Institute of Inorganic Chemistry, RWTH Aachen University, Aachen, 52056 Germany

9. Oana Cojocaru‐Mirédin Aachen Institute of Physics IA

   RWTH Aachen University

   Affiliation as printed

   Institute of Physics IA RWTH Aachen University Aachen 52074 Germany

   Institute of Physics IA, RWTH Aachen University, Aachen, 52074 Germany

10. Jean‐Yves Raty

    University of Liège · Commissariat à l'Énergie Atomique et aux Énergies Alternatives · CEA Grenoble · Laboratoire d'Électronique des Technologies de l'Information · Université Grenoble Alpes

    Affiliation as printed

    CESAM and Physics of Solids Interfaces and Nanostructures, B5 Université de Liège Sart‐Tilman B4000 Belgium

    UGA CEA‐LETI MINATEC Campus 17 rue des Martyrs Grenoble Cedex 9 F 38054 France

    UGA, CEA-LETI, MINATEC Campus, 17 rue des Martyrs, Grenoble Cedex 9, F 38054 France

11. Matthias Wuttig corresponding Aachen Institute of Physics IA JARA-FIT Institute Green-IT

    Forschungszentrum Jülich · Jülich Aachen Research Alliance · RWTH Aachen University

    Affiliation as printed

    Institute of Physics IA RWTH Aachen University Aachen 52074 Germany

    JARA‐FIT Institute Green‐IT RWTH Aachen University and Forschungszentrum Jülich Aachen 52056 Germany

    Jülich‐Aachen Research Alliance (JARA‐HPC) RWTH Aachen University Aachen 52056 Germany

    Institute of Physics IA, RWTH Aachen University, Aachen, 52074 Germany