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

arXiv (Cornell University)

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.

Authors 10

1. Stefan Maier Aachen Institute of Physics IA Institute of Physics (IA)

   RWTH Aachen University

   Affiliation as printed

   Institute of Physics IA , RWTH Aachen University , 52074 Aachen , 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 , 52056 Aachen , Germany

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

3. Yudong Cheng Aachen Institute of Physics IA Institute of Physics (IA)

   RWTH Aachen University

   Affiliation as printed

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

   Institute of Physics (IA) RWTH Aachen University Aachen 52074 Germany

4. Carl‐Friedrich Schön Aachen Institute of Physics IA Institute of Physics (IA)

   RWTH Aachen University

   Affiliation as printed

   Institute of Physics IA , RWTH Aachen University , 52074 Aachen , 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 , 52056 Aachen , 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 , 52056 Aachen , Germany

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

   Jülich-Aachen Research Alliance (JARA-HPC), 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 , 182 23 Prague 8 , Czech Republic

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

8. Oana Cojocaru‐Mirédin Aachen Institute of Physics IA Institute of Physics (IA)

   RWTH Aachen University

   Affiliation as printed

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

   Institute of Physics (IA) RWTH Aachen University Aachen 52074 Germany

9. Jean‐Yves Raty

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

   Affiliation as printed

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

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

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

10. Matthias Wuttig Aachen

    Jülich Aachen Research Alliance · RWTH Aachen University

    Affiliation as printed

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