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Activation of Semicore Electrons in Alkali Metals and Their Role in the B1-B2 Phase Transition under Pressure.

作者信息

Racioppi Stefano, Zurek Eva

机构信息

Department of Chemistry, State University of New York at Buffalo, 777 Natural Science Complex, Buffalo, New York 14260-3000, United States.

出版信息

J Am Chem Soc. 2025 Sep 10;147(36):32745-32751. doi: 10.1021/jacs.5c08582. Epub 2025 Aug 25.

Abstract

Alkali fluorides are often thought of as archetypical ionic compounds whose structures can be understood in terms of the packing of rigid spheres. At ambient pressure, they assume the rocksalt (B1) structure, while under only a few GPa of pressure, the cesium chloride (B2) structure, with higher coordination numbers, is assumed for KF, RbF, and CsF. NaF requires almost 10 times more pressure to undergo this same phase transition, which has not been observed for LiF. Herein, we provide a detailed analysis, based upon quantum chemical calculations, explaining this behavior. We show that for the heavier alkali metals, the semicore p orbitals engage in metal-metal bonding in the B2 phase, facilitating the pressure-induced B1 → B2 structural transition. These findings suggest that the semicore orbitals of heavy alkali metals can be activated without the need of strong oxidants at very mild levels of compression, resulting in the formation of chemical bonds, challenging both traditional and modern core-valence distinctions. In addition, we argue that Cs 5p-5p bonding in CsCl occurs already at ambient pressure, stabilizing the B2 phase, and suggest experiments that may be able to detect signatures of such bonding.

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