[en] 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.
Disciplines :
Physics
Author, co-author :
Maier, Stefan
Steinberg, Simon
Cheng, Yudong
Schön, Carl-Friedrich
Schumacher, Mathias
Mazzarello, Riccardo
Golub, Pavlo
Nelson, Ryky
Cojocaru-Mirédin, Oana
Raty, Jean-Yves ; Université de Liège - ULiège > Département de physique > Physique des solides, interfaces et nanostructures
Wuttig, Matthias
Language :
English
Title :
Discovering Electron-Transfer-Driven Changes in Chemical Bonding in Lead Chalcogenides (PbX, where X = Te, Se, S, O)
Publication date :
2020
Journal title :
Advanced Materials
ISSN :
0935-9648
eISSN :
1521-4095
Publisher :
Wiley-Blackwell, United States
Volume :
32
Issue :
49
Pages :
2005533
Peer reviewed :
Peer Reviewed verified by ORBi
Tags :
Tier-1 supercomputer CÉCI : Consortium des Équipements de Calcul Intensif
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