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.

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

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

Institute of Inorganic Chemistry RWTH Aachen University Aachen 52056 Germany

Institute of Physics IA RWTH Aachen University Aachen 52074 Germany

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

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

Jülich Aachen Research Alliance RWTH Aachen University Aachen 52056 Germany

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

Zobrazit více v PubMed

R. Hoffmann, Angew. Chem., Int. Ed. Engl. 1987, 26, 846.

G. J. Miller, Eur. J. Inorg. Chem. 1998, 1998, 523.

K. Shportko, S. Kremers, M. Woda, D. Lencer, J. Robertson, M. Wuttig, Nat. Mater. 2008, 7, 653.

M. Wuttig, D. Lüsebrink, D. Wamwangi, W. Welnic, M. Gilleßen, R. Dronskowski, Nat. Mater. 2007, 6, 122.

D. Lencer, M. Salinga, B. Grabowski, T. Hickel, J. Neugebauer, M. Wuttig, Nat. Mater. 2008, 7, 972.

V. L. Deringer, W. Zhang, M. Lumeij, S. Maintz, M. Wuttig, R. Mazzarello, R. Dronskowski, Angew. Chem., Int. Ed. 2014, 53, 10817.

V. L. Deringer, R. Dronskowski, M. Wuttig, Adv. Funct. Mater. 2015, 25, 6343.

Y. Yu, M. Cagnoni, O. Cojocaru-Miredin, M. Wuttig, Adv. Funct. Mater. 2019, 30, 1904862.

W. G. Zeier, A. Zevalkink, Z. M. Gibbs, G. Hautier, M. G. Kanatzidis, G. J. Snyder, Angew. Chem., Int. Ed. 2016, 55, 6826.

L. Pauling, The Nature of the Chemical Bond, Cornell University Press, New York 1960.

C. Coulson, Coulson's Valence, Oxford University Press, Oxford, UK 1979.

L. Pauling, Nature 1980, 284, 685.

M. Springborg, Y. Dong, in Handbook of Solid State Chemistry (Eds: R. Dronskowski, S. Kikkawa, A. Stein), Wiley-VCH GmbH & Co. KGaA, Weinheim, Germany 2017.

K. Schwarz, P. Blaha, in Hanbook of Solid State Chemistry (Eds: R. Dronskowski, S. Kikkawa, A. Stein), Wiley-VCH GmbH & Co KGaA, Weinheim, Germany 2017.

A. Moewes, in Handbook of Solid State Chemistry (Eds: R. Dronskowski, S. Kikkawa, A. Stein), Wiley-VCH GmbH & Co. KGaA, Weinheim, Germany 2017.

M. Wuttig, V. L. Deringer, X. Gonze, C. Bichara, J.-Y. Raty, Adv. Mater. 2018, 30, 1803777.

J.-Y. Raty, M. Schumacher, P. Golub, V. L. Deringer, C. Gatti, M. Wuttig, Adv. Mater. 2019, 31, 1806280.

M. Zhu, O. Cojocaru-Miredin, A. M. Mio, J. Keutgen, M. Kupers, Y. Yu, J. Y. Cho, R. Dronskowski, M. Wuttig, Adv. Mater. 2018, 30, 1706735.

Y. Cheng, O. Cojocaru-Mirédin, J. Keutgen, Y. Yu, M. Küpers, M. Schumacher, P. Golub, J.-Y. Raty, R. Dronskowski, M. Wuttig, Adv. Mater. 2019, 31, 1904316.

L. Guarneri, S. Jakobs, A. von Hoegen, S. Maier, O. Cojocaru-Mirédin, M. Raghuwanshi, M. Drögeler, C. Stampfer, R. P. S. M. Lobo, A. Piarristeguy, A. Pradel, M. Xu, M. Wuttig, ArXiv: 2008.10219 [cond-mat.mtrl-sci] 2020.

The phrase ‘iono-covalent bonding’ is employed here to describe bonds with both significant ionic and covalent bonding contribution, i.e. covalent bonds with significant polar bond contributions, or ionic bonds with a pronounced covalent contribution. We do not consider iono-covalent bonding as a distinct and fundamental bonding mechanism. Instead the term is employed to describe the transition region from covalent to ionic bonding.

G. J. Snyder, E. S. Toberer, Nat. Mater. 2008, 7, 105.

J. R. Sootsman, D. Y. Chung, M. G. Kanatzidis, Angew. Chem., Int. Ed. 2009, 48, 8616.

P. Garnier, J. Moreau, J. R. Gavarri, Mater. Res. Bull. 1990, 25, 979.

S. Katayama, H. Kawamura, Solid State Commun. 1977, 21, 521.

T. S. Moss, Proc. Phys. Soc., London, Sect. B 1950, 63, 167.

B. J. Kooi, M. Wuttig, Adv. Mater. 2020, 32, 1908302.

R. Hoppe, Z. Kristallogr. 1979, 150, 23.

J. S. Dugdale, D. K. C. Macdonald, Phys. Rev. 1955, 98, 1751.

N. Amirifar, R. Lardé, E. Talbot, P. Pareige, L. Rigutti, L. Mancini, J. Houard, C. Castro, V. Sallet, E. Zehani, S. Hassani, C. Sartel, A. Ziani, X. Portier, J. Appl. Phys. 2015, 118, 215703.

L. Yao, B. Gault, J. M. Cairney, S. P. Ringer, Philos. Mag. Lett. 2010, 90, 121.

L. C. Allen, J. F. Capitani, G. A. Kolks, G. D. Sproul, J. Mol. Struct. 1993, 300, 647.

M. Esser, S. Maintz, R. Dronskowski, J. Comput. Chem. 2017, 38, 620.

W. Welnic, S. Botti, L. Reining, M. Wuttig, Phys. Rev. Lett. 2007, 98, 236403.

M. Wuttig, C.-F. Schön, 2019, https://www.institut-1a.physik.rwth-aachen.de/cms/INSTITUT-1A/Das-Institut/Meldungen/~hgatt/Veroeffentlichung-einer-interaktiven-Mat/?lidx=1 (accessed: October 2020).

Y. Wu, P. Nan, Z. Chen, Z. Zeng, S. Lin, X. Zhang, H. Dong, Z. Chen, H. Gu, W. Li, Y. Chen, B. Ge, Y. Pei, Research 2020, 8151059.

G. Tan, M. Ohta, M. G. Kanatzidis, Phil. Trans. R. Soc. A 2019, 377, 20180450.

C. Gayner, K. K. Kar, W. Kim, Mater. Today Energy 2018, 9, 359.

M. Cagnoni, D. Fuhren, M. Wuttig, Adv. Mater. 2018, 30, 1801787.

M. E. X. Wang, Structural Features and Thermoelectric Properties of PbTe-Based Materials, Dissertation (Doctor rerum naturalium), Technische Universität Dresden, Dresden, Germany 2019, https://nbn-resolving.org/urn:nbn:de:bsz:14-qucosa2-340289.

C. Gayner, K. K. Kar, Prog. Mater. Sci. 2016, 83, 330.

Y. Noda, S. Ohba, S. Sato, Y. Saito, Acta Crystallogr. B 1983, 39, 312.

P. E. Blöchl, Phys. Rev. B: Condens. Matter Mater. Phys. 1994, 50, 17953.

G. Kresse, M. Marsman, J. Furthmüller, Vienna Ab Initio Simulation Package (VASP), The Guide, Computational Materials Physics, Faculty of Physics, Universität Wien, Vienna, Austria 2014.

G. Kresse, J. Furthmüller, Phys. Rev. B: Condens. Matter Mater. Phys. 1996, 54, 11169.

G. Kresse, J. Hafner, Phys. Rev. B: Condens. Matter Mater. Phys. 1993, 47, 558.

G. Kresse, D. Joubert, Phys. Rev. B: Condens. Matter Mater. Phys. 1999, 59, 1758.

X. Gonze, B. Amadon, P.-M. Anglade, J.-M. Beuken, F. Bottin, P. Boulanger, F. Bruneval, D. Calistae, R. Caracas, M. Coté, T. Deutsch, L. Genovese, P. Ghosez, M. Giantomassi, S. Goedecker, D. R. Haman, P. Hermet, F. Jollet, G. Jomard, S. Leroux, M. Mancini, S. Mazevet, M. J. T. Oliveira, G. Onida, Y. Pouillon, T. Rangel, G.-M. Rignanese, D. Sangalli, R. Shaltaf, M. Torrent, M. J. Verstraete, G. Zerah, J. W. Zwanziger, Comput. Phys. Commun. 2009, 180, 2582.

M. Torrent, F. Jollet, F. Bottin, G. Zerah, X. Gonze, Comput. Mater. Sci. 2008, 42, 337.

J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 1996, 77, 3865.

M. Yu, D. R. Trinkle, J. Chem. Phys. 2011, 134, 064111.

M. Kohout, DGrid, version 4.6, Radebeul, Germany 2011.

R. F. W. Bader, M. E. Stephens, J. Am. Chem. Soc. 1975, 97, 7391.

X. Fradera, M. A. Austen, R. F. W. Bader, J. Phys. Chem. A 1999, 103, 304.

Metavalent or Hypervalent Bonding: Is There a Chance for Reconciliation?