Unraveling Multicenter Chemical Bonding in Electron-Rich Solids (with the help of high pressure studies)
ORAL
Abstract
Multicenter chemical bonding plays a crucial role in understanding the structural and electronic properties of materials with electron-rich elements (pnictogens, chalcogens, halogens, and related compounds). In this contribution, we present a unified theory of electron-rich multicenter bonds (ERMBs) and electron-deficient multicenter bonds (EDMBs), demonstrating that both types of multicenter bonds share a common origin but differ in their formation mechanisms on increasing the electronic density (by pressure, reduction, or chemical substitution).1,2
We provide theoretical evidence that the unconventional bonding found in phase-change materials (PCMs), often described as resonant p-type covalent, metavalent,3,4 or hypervalent,5,6 indeed corresponds to EDMBs. We extend EDMBs beyond PCMs, showing that EDMBs emerge in high-pressure phases of many materials including elemental hydrogen in the limit of 500 GPa. Moreover, we propose that ERMBs primarily occur as linear or quasi-linear three-center-four-electron (3c-4e) bonds, while EDMBs manifest as three-center-two-electron (3c-2e) bonds in molecules and as linear or quasi-linear two-center-one-electron (2c-1e) bonds in extended solids. This new perspective challenges existing paradigms in chemical bonding theory and introduces a novel notation for hypercoordinated multicenter units in molecules and solids. Our work provides a deeper understanding of the fundamental nature of multicenter bonding, paving the way for new interpretations of structure-property relationships in advanced materials.
[1] H.H. Osman et al. J. Mater. Chem. C 12, 10447 (2024).
[2] H.H. Osman et al. J. Mater. Chem. C JUST ACCEPTED (2025), https://doi.org/10.1039/D4TC04441J
[3] M. Wuttig et al. Adv. Mater. 30, 1803777 (2018).
[4] J.-Y. Raty et al. Adv. Mater. 31, 1806280 (2019).
[5] T. H. Lee, S. R. Elliott, Adv. Mater. 32, 2000340 (2020).
[6] J. Hempelmann et al. Adv. Mater. 33, 2100163 (2021).
We provide theoretical evidence that the unconventional bonding found in phase-change materials (PCMs), often described as resonant p-type covalent, metavalent,3,4 or hypervalent,5,6 indeed corresponds to EDMBs. We extend EDMBs beyond PCMs, showing that EDMBs emerge in high-pressure phases of many materials including elemental hydrogen in the limit of 500 GPa. Moreover, we propose that ERMBs primarily occur as linear or quasi-linear three-center-four-electron (3c-4e) bonds, while EDMBs manifest as three-center-two-electron (3c-2e) bonds in molecules and as linear or quasi-linear two-center-one-electron (2c-1e) bonds in extended solids. This new perspective challenges existing paradigms in chemical bonding theory and introduces a novel notation for hypercoordinated multicenter units in molecules and solids. Our work provides a deeper understanding of the fundamental nature of multicenter bonding, paving the way for new interpretations of structure-property relationships in advanced materials.
[1] H.H. Osman et al. J. Mater. Chem. C 12, 10447 (2024).
[2] H.H. Osman et al. J. Mater. Chem. C JUST ACCEPTED (2025), https://doi.org/10.1039/D4TC04441J
[3] M. Wuttig et al. Adv. Mater. 30, 1803777 (2018).
[4] J.-Y. Raty et al. Adv. Mater. 31, 1806280 (2019).
[5] T. H. Lee, S. R. Elliott, Adv. Mater. 32, 2000340 (2020).
[6] J. Hempelmann et al. Adv. Mater. 33, 2100163 (2021).
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Publication: [1] H.H. Osman, A. Otero-de-la-Roza, P. Rodríguez-Hernández, A. Muñoz, F.J. Manjón, J. Mater. Chem. C 12, 10447 (2024).<br>[2] H.H. Osman, P. Rodríguez-Hernández, A. Muñoz, F.J. Manjón, J. Mater. Chem. C JUST ACCEPTED (2025), https://doi.org/10.1039/D4TC04441J
Presenters
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Francisco Javier Manjón Herrera
Universitat Politècnica de València
Authors
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Francisco Javier Manjón Herrera
Universitat Politècnica de València
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Hussien H Osman
Universitat de València
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Plácida Rodríguez-Hernández
Universidad de La Laguna
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Alfonso Muñoz
Universidad de La Laguna