Metavalent bonding in crystalline solids: how does it collapse?

arXiv (Cornell University)

Abstract

The chemical bond is one of the most powerful, yet controversial concepts in chemistry, explaining property trends in solids. Recently, a novel type of chemical bonding has been identified in several higher chalcogenides, characterized by a unique property portfolio, unconventional bond breaking and sharing of about one electron between adjacent atoms. Metavalent bonding is a fundamental type of bonding besides covalent, ionic and metallic bonding, raising the pertinent question, if there is a well-defined transition between metavalent and covalent bonding. For three different pseudo-binary lines, namely GeTe1-xSex, Sb2Te3(1-x)Se3x and Bi2-2xSb2xSe3, a sudden drop in several properties, including the optical dielectric constant, the Born effective charge, the electrical conductivity as well as the bond breaking is observed once a critical Se or Sb concentration is reached. This finding provides a blueprint to explore the impact of metavalent bonding on attractive properties utilized in phase change materials and thermoelectrics.

Authors 13

1. Ludovica Guarneri Aachen I. Physikalisches Institut

   RWTH Aachen University

   Affiliation as printed

   RWTH Aachen University , I. Physikalisches Institut (IA) , 52056 Aachen , Germany

2. Stefan Jakobs Aachen I. Physikalisches Institut

   RWTH Aachen University

   Affiliation as printed

   RWTH Aachen University , I. Physikalisches Institut (IA) , 52056 Aachen , Germany

3. Alexander von Hoegen Aachen I. Physikalisches Institut

   RWTH Aachen University

   Affiliation as printed

   RWTH Aachen University , I. Physikalisches Institut (IA) , 52056 Aachen , Germany

4. Stefan Maier Aachen I. Physikalisches Institut

   RWTH Aachen University

   Affiliation as printed

   RWTH Aachen University , I. Physikalisches Institut (IA) , 52056 Aachen , Germany

5. Oana Cojocaru‐Mirédin Aachen I. Physikalisches Institut

   RWTH Aachen University

   Affiliation as printed

   RWTH Aachen University , I. Physikalisches Institut (IA) , 52056 Aachen , Germany

6. Mohit Raghuwanshi Aachen I. Physikalisches Institut

   RWTH Aachen University

   Affiliation as printed

   RWTH Aachen University , I. Physikalisches Institut (IA) , 52056 Aachen , Germany

7. Marc Drögeler Aachen II. Physikalisches Institut (IIA)

   RWTH Aachen University

   Affiliation as printed

   RWTH Aachen University , II. Physikalisches Institut (IIA) , 52056 Aachen , Germany

8. Christoph Stampfer Aachen JARA‐FIT and JARA‐HPC II. Physikalisches Institut (IIA)

   RWTH Aachen University

   Affiliation as printed

   JARA-FIT and JARA-HPC , RWTH Aachen University , 52056 Aachen , Germany

   RWTH Aachen University , II. Physikalisches Institut (IIA) , 52056 Aachen , Germany

9. R. P. S. M. Lobo

   Centre National de la Recherche Scientifique · Université Paris Sciences et Lettres · Sorbonne Université · ESPCI Paris

   Affiliation as printed

   LPEM , ESPCI Paris , CNRS , PSL University ; 10 rue Vauquelin , F-75005 Paris , France

   Sorbonne Université , ESPCI Paris , CNRS , LPEM , F-75005 Paris , France

10. Andrea A. Piarristeguy

    Centre National de la Recherche Scientifique · Institut Charles Gerhardt Montpellier

    Affiliation as printed

    Institut Charles Gerhardt , UMR CNRS 5253 , Univ. Montpellier , F-34095 Montpellier , France

11. A. Pradel

    Centre National de la Recherche Scientifique · Institut Charles Gerhardt Montpellier

    Affiliation as printed

    Institut Charles Gerhardt , UMR CNRS 5253 , Univ. Montpellier , F-34095 Montpellier , France

12. Meng Kai Xu Aachen I. Physikalisches Institut

    RWTH Aachen University

    Affiliation as printed

    RWTH Aachen University , I. Physikalisches Institut (IA) , 52056 Aachen , Germany

13. Matthias Wuttig