On the Electride Nature of Na-hP4.
Alkali Metals
Chemical Bonding
Electride
High Pressure
Sodium
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
27 Nov 2023
27 Nov 2023
Historique:
received:
27
07
2023
medline:
5
10
2023
pubmed:
5
10
2023
entrez:
5
10
2023
Statut:
ppublish
Résumé
Early quantum mechanical models suggested that pressure drives solids towards free-electron metal behavior where the ions are locked into simple close-packed structures. The prediction and subsequent discovery of high-pressure electrides (HPEs), compounds assuming open structures where the valence electrons are localized in interstitial voids, required a paradigm shift. Our quantum chemical calculations on the iconic insulating Na-hP4 HPE show that increasing density causes a 3s→3pd electronic transition due to Pauli repulsion between the 1s2s and 3s states, and orthogonality of the 3pd states to the core. The large lobes of the resulting Na-pd hybrid orbitals point towards the center of an 11-membered penta-capped trigonal prism and overlap constructively, forming multicentered bonds, which are responsible for the emergence of the interstitial charge localization in Na-hP4. These multicentered bonds facilitate the increased density of this phase, which is key for its stabilization under pressure.
Identifiants
pubmed: 37796438
doi: 10.1002/anie.202310802
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
e202310802Subventions
Organisme : National Science Foundation
ID : PHY-2020249
Organisme : Engineering and Physical Sciences Research Council
ID : EP/R02927X/1
Organisme : Engineering and Physical Sciences Research Council
ID : EP/S022155/1
Organisme : U.S. Department of Energy, Office of Science, Fusion Energy Sciences
ID : DE-SC0020340
Informations de copyright
© 2023 Wiley-VCH GmbH.
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