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1. Synthesis, Elasticity, and Spin State of an Intermediate MgSiO 3 ‐FeAlO 3 Bridgmanite: Implications for Iron in Earth's Lower Mantle

   https://doi.org/10.1029/2020JB019964  

   Zhu, Feng ; Liu, Jiachao ; Lai, Xiaojing ; Xiao, Yuming ; Prakapenka, Vitali ; Bi, Wenli ; Alp, E. Ercan ; Dera, Przemyslaw ; Chen, Bin ; Li, Jie ( July 2020 , Journal of Geophysical Research: Solid Earth)

   Fe‐Al‐bearing bridgmanite may be the dominant host for ferric iron in Earth's lower mantle. Here we report the synthesis of (Mg_0.5Fe³⁺_0.5)(Al_0.5Si_0.5)O₃bridgmanite (FA50) with the highest Fe³⁺‐Al³⁺coupled substitution known to date. X‐ray diffraction measurements showed that at ambient conditions, the FA50 adopted the LiNbO₃structure. Upon compression at room temperature to 18 GPa, it transformed back into the bridgmanite structure, which remained stable up to 102 GPa and 2,600 K. Fitting Birch‐Murnaghan equation of state of FA50 bridgmanite yieldsV₀ = 172.1(4) ų,K₀ = 229(4) GPa withK₀′ = 4(fixed). The calculated bulk sound velocity of the FA50 bridgmanite is ~7.7% lower than MgSiO₃bridgmanite, mainly because the presence of ferric iron increases the unit‐cell mass by 15.5%. This difference likely represents the upper limit of sound velocity anomaly introduced by Fe³⁺‐Al³⁺substitution. X‐ray emission and synchrotron Mössbauer spectroscopy measurements showed that after laser annealing, ~6% of Fe³⁺cations exchanged with Al³⁺and underwent the high‐ to low‐spin transition at 59 GPa. The low‐spin proportion of Fe³⁺increased gradually with pressure and reached 17–31% at 80 GPa. Since the cation exchange and spin transition in this Fe³⁺‐Al³⁺‐enriched bridgmanite do not cause resolvable unit‐cell volume reduction, and the increase of low‐spin Fe³⁺fraction with pressure occurs gradually, the spin transition would not produce a distinct seismic signature in the lower mantle. However, it may influence iron partitioning and isotopic fractionation, thus introducing chemical heterogeneity in the lower mantle.

    

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2. Spin Transitions and Compressibility of ε‐Fe 7 N 3 and γ′‐Fe 4 N: Implications for Iron Alloys in Terrestrial Planet Cores

   https://doi.org/10.1029/2020JB020660  

   Lv, Mingda ; Liu, Jiachao ; Zhu, Feng ; Li, Jie ; Zhang, Dongzhou ; Xiao, Yuming ; Dorfman, Susannah M. ( November 2020 , Journal of Geophysical Research: Solid Earth)

   Iron nitrides are possible constituents of the cores of Earth and other terrestrial planets. Pressure‐induced magnetic changes in iron nitrides and effects on compressibility remain poorly understood. Here we report synchrotron X‐ray emission spectroscopy (XES) and X‐ray diffraction (XRD) results for ε‐Fe₇N₃and γ′‐Fe₄N up to 60 GPa at 300 K. The XES spectra reveal completion of high‐ to low‐spin transition in ε‐Fe₇N₃and γ′‐Fe₄N at 43 and 34 GPa, respectively. The completion of the spin transition induces stiffening in bulk modulus of ε‐Fe₇N₃by 22% at ~40 GPa, but has no resolvable effect on the compression behavior of γ′‐Fe₄N. Fitting pressure‐volume data to the Birch‐Murnaghan equation of state yieldsV₀ = 83.29 ± 0.03 (ų),K₀ = 232 ± 9 GPa,K₀′ = 4.1 ± 0.5 for nonmagnetic ε‐Fe₇N₃above the spin transition completion pressure, andV₀ = 54.82 ± 0.02 (ų),K₀ = 152 ± 2 GPa,K₀′ = 4.0 ± 0.1 for γ′‐Fe₄N over the studied pressure range. By reexamining evidence for spin transition and effects on compressibility of other candidate components of terrestrial planet cores, Fe₃S, Fe₃P, Fe₇C₃, and Fe₃C based on previous XES and XRD measurements, we located the completion of high‐ to low‐spin transition at ~67, 38, 50, and 30 GPa at 300 K, respectively. The completion of spin transitions of Fe₃S, Fe₃P, and Fe₃C induces elastic stiffening, whereas that of Fe₇C₃induces elastic softening. Changes in compressibility at completion of spin transitions in iron‐light element alloys may influence the properties of Earth's and planetary cores.

    

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3. Drastic enhancement of magnetic critical temperature and amorphization in topological magnet EuSn2P2 under pressure

   https://doi.org/10.1038/s41535-022-00451-9  

   Bi, Wenli ; Culverhouse, Trenton ; Nix, Zachary ; Xie, Weiwei ; Tien, Hung-Ju ; Chang, Tay-Rong ; Dutta, Utpal ; Zhao, Jiyong ; Lavina, Barbara ; Alp, Esen E. ; et al ( December 2022 , npj Quantum Materials)

   Abstract High pressure is an effective tool to induce exotic quantum phenomena in magnetic topological insulators by controlling the interplay of magnetic order and topological state. This work presents a comprehensive high-pressure study of the crystal structure and magnetic ground state up to 62 GPa in an intrinsic topological magnet EuSn 2 P 2 . With a combination of high resolution X-ray diffraction, 151 Eu synchrotron Mössbauer spectroscopy, X-ray absorption spectroscopy, molecular orbital calculations, and electronic band structure calculations, it has been revealed that pressure drives EuSn 2 P 2 from a rhombohedral crystal to an amorphous phase at 36 GPa accompanied by a fourfold enhancement of magnetic ordering temperature. In the pressure-induced amorphous phase, Eu ions take an intermediate valence state. The drastic enhancement of magnetic ordering temperature from 30 K at ambient pressure to 130 K at 41.2 GPa resulting from Ruderman–Kittel–Kasuya–Yosida (RKKY) interactions likely attributes to the stronger Eu–Sn interaction at high pressure. These rich results demonstrate that EuSn 2 P 2 is an ideal platform to study the correlation of the enhanced RKKY interactions, disordered lattice, intermediate valence, and topological state. 

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4. Pressure-induced shift of effective Ce valence, Fermi energy and phase boundaries in CeOs 4 Sb 12

   https://doi.org/10.1088/1367-2630/ac643c  

   Götze, K. ; Pearce, M. J. ; Coak, M. J. ; Goddard, P. A. ; Grockowiak, A. D. ; Coniglio, W. A. ; Tozer, S. W. ; Graf, D. E. ; Maple, M. B. ; Ho, P-C ; et al ( April 2022 , New Journal of Physics)

   CeOs₄Sb₁₂, a member of the skutterudite family, has an unusual semimetallic low-temperature$\mathcal{L}$-phase that inhabits a wedge-like area of the fieldH—temperatureTphase diagram. We have conducted measurements of electrical transport and megahertz conductivity on CeOs₄Sb₁₂single crystals under pressures of up to 3 GPa and in high magnetic fields of up to 41 T to investigate the influence of pressure on the differentH–Tphase boundaries. While the high-temperature valence transition between the metallic$\mathcal{H}$-phase and the$\mathcal{L}$-phase is shifted to higherTby pressures of the order of 1 GPa, we observed only a marginal suppression of the$\mathcal{S}$-phase that is found below 1 K for pressures of up to 1.91 GPa. High-field quantum oscillations have been observed for pressures up to 3.0 GPa and the Fermi surface of the high-field side of the$\mathcal{H}$-phase is found to show a surprising decrease in size with increasing pressure, implying a change in electronic structure rather than a mere contraction of lattice parameters. We evaluate the field-dependence of the effective masses for different pressures and also reflect on the sample dependence of some of the properties of CeOs₄Sb₁₂which appears to be limited to the low-field region.

    

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5. Enhanced Néel temperature in EuSnP under pressure

   https://doi.org/10.1039/c9dt00449a  

   Gui, Xin ; Finkelstein, Gregory J. ; Graf, David E. ; Wei, Kaya ; Zhang, Dongzhou ; Baumbach, Ryan E. ; Dera, Przemyslaw ; Xie, Weiwei ( April 2019 , Dalton Transactions)

   We present the combined results of single crystal X-ray diffraction, physical properties characterization, and theoretical assessment of EuSnP under high pressure. Single crystals of EuSnP prepared using Sn self-flux crystallize in the tetragonal NbCrN-type crystal structure (S.G. P 4/ nmm ) at ambient pressure. Previous studies have shown that for Eu ions, seven unpaired electrons impart a 2+ oxidation state. Assuming the oxidation states of Eu to be +2 and P to be −3, each Sn will donate one electron, with one p valence electron left for forming a weak Sn–Sn bond. According to the high-pressure single crystal X-ray diffraction measurements, no structural phase transition was observed up to ∼6.2 GPa. Temperature-dependent resistivity measurements up to 2.15 GPa on single crystals indicate that the phase-transition temperature occurring at the Néel temperature ( T N ) is significantly enhanced under high pressure. The robust crystallography and enhanced antiferromagnetic transition temperatures can be rationalized by the electronic structure calculations and chemical bonding analysis. The increasing Eu–P bonding interaction is consistent with the lattice parameter changing and enhanced T N . Moreover, the molecular orbital diagram shows that the weak Sn–Sn bond can be squeezed under pressure, acting as a compression buffer to stabilize the structure. 

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