First-principles theory for cerium predicts three distinct face-centered cubic phases

Abstract We show results from first-principles calculations for cerium at very high compressions. These reveal a most remarkable behavior in a material; depending on atomic volume, cerium adopts three distinct face-centered cubic (fcc) phases driven by different physical mechanisms. The two well-kno...

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Main Authors: Per Söderlind, Alexander Landa, Christine Wu, Damian Swift, Börje Johansson
Format: Article
Language:English
Published: Nature Portfolio 2025-05-01
Series:Scientific Reports
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Online Access:https://doi.org/10.1038/s41598-025-03174-6
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author Per Söderlind
Alexander Landa
Christine Wu
Damian Swift
Börje Johansson
author_facet Per Söderlind
Alexander Landa
Christine Wu
Damian Swift
Börje Johansson
author_sort Per Söderlind
collection DOAJ
description Abstract We show results from first-principles calculations for cerium at very high compressions. These reveal a most remarkable behavior in a material; depending on atomic volume, cerium adopts three distinct face-centered cubic (fcc) phases driven by different physical mechanisms. The two well-known a and phases are vigorously debated in the literature, but we focus on the a phase as a metal with delocalized character of the 4f electron. The ultimate high compression fcc phase, here named ω, is driven partly by electrostatics. Our density-functional theory (DFT) study excellently reproduces the experimentally known compression behavior of cerium up to a few Mbar but goes beyond those pressures with structural transitions to tetragonal, hexagonal, and cubic (fcc) phases occurring before 100 Mbar (10000 GPa or 10 TPa). The 4f-electron contribution to the chemical bonding is shown to rule phase transitions and compressibility. The change of 4f occupation nicely explains the pressure dependence of the structural axial ratio in the tetragonal phase. At very high pressure, structures known at low pressures return because of band broadening, electrostatic ion repulsion, and an increase in hybridization between states that under normal conditions can be considered core (atomic like) states and the valence-band states.
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spelling doaj-art-a707ea8941c2441c8e903d5dbbba4d822025-08-20T03:22:09ZengNature PortfolioScientific Reports2045-23222025-05-0115111110.1038/s41598-025-03174-6First-principles theory for cerium predicts three distinct face-centered cubic phasesPer Söderlind0Alexander Landa1Christine Wu2Damian Swift3Börje Johansson4Lawrence Livermore National LaboratoryLawrence Livermore National LaboratoryLawrence Livermore National LaboratoryLawrence Livermore National LaboratoryDivision of Materials Theory, Department of Physics and Astronomy, Uppsala UniversityAbstract We show results from first-principles calculations for cerium at very high compressions. These reveal a most remarkable behavior in a material; depending on atomic volume, cerium adopts three distinct face-centered cubic (fcc) phases driven by different physical mechanisms. The two well-known a and phases are vigorously debated in the literature, but we focus on the a phase as a metal with delocalized character of the 4f electron. The ultimate high compression fcc phase, here named ω, is driven partly by electrostatics. Our density-functional theory (DFT) study excellently reproduces the experimentally known compression behavior of cerium up to a few Mbar but goes beyond those pressures with structural transitions to tetragonal, hexagonal, and cubic (fcc) phases occurring before 100 Mbar (10000 GPa or 10 TPa). The 4f-electron contribution to the chemical bonding is shown to rule phase transitions and compressibility. The change of 4f occupation nicely explains the pressure dependence of the structural axial ratio in the tetragonal phase. At very high pressure, structures known at low pressures return because of band broadening, electrostatic ion repulsion, and an increase in hybridization between states that under normal conditions can be considered core (atomic like) states and the valence-band states.https://doi.org/10.1038/s41598-025-03174-6CeriumCrystal structureHigh pressureUnique metal
spellingShingle Per Söderlind
Alexander Landa
Christine Wu
Damian Swift
Börje Johansson
First-principles theory for cerium predicts three distinct face-centered cubic phases
Scientific Reports
Cerium
Crystal structure
High pressure
Unique metal
title First-principles theory for cerium predicts three distinct face-centered cubic phases
title_full First-principles theory for cerium predicts three distinct face-centered cubic phases
title_fullStr First-principles theory for cerium predicts three distinct face-centered cubic phases
title_full_unstemmed First-principles theory for cerium predicts three distinct face-centered cubic phases
title_short First-principles theory for cerium predicts three distinct face-centered cubic phases
title_sort first principles theory for cerium predicts three distinct face centered cubic phases
topic Cerium
Crystal structure
High pressure
Unique metal
url https://doi.org/10.1038/s41598-025-03174-6
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