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1. Strong enhancement of magnetic ordering temperature and structural/valence transitions in EuPd ₃ S ₄ under high pressure

   https://doi.org/10.1073/pnas.2310779120  

   Huyan, Shuyuan; Ryan, Dominic H.; Slade, Tyler J.; Lavina, Barbara; Jose, Greeshma; Wang, Haozhe; Wilde, John M.; Ribeiro, Raquel A.; Zhao, Jiyong; Xie, Weiwei; et al (December 2023, Proceedings of the National Academy of Sciences)

   We present a comprehensive study of the inhomogeneous mixed-valence compound, EuPd₃S₄, by electrical transport, X-ray diffraction, time-domain¹⁵¹Eu synchrotron Mössbauer spectroscopy, and X-ray absorption spectroscopy measurements under high pressure. Electrical transport measurements show that the antiferromagnetic ordering temperature,T_N, increases rapidly from 2.8 K at ambient pressure to 23.5 K at ~19 GPa and plateaus between ~19 and ~29 GPa after which no anomaly associated withT_Nis detected. A pressure-induced first-order structural transition from cubic to tetragonal is observed, with a rather broad coexistence region (~20 GPa to ~30 GPa) that corresponds to theT_Nplateau. Mössbauer spectroscopy measurements show a clear valence transition from approximately 50:50 Eu²⁺:Eu³⁺to fully Eu³⁺at ~28 GPa, consistent with the vanishing of the magnetic order at the same pressure. X-ray absorption data show a transition to a fully trivalent state at a similar pressure. Our results show that pressure first greatly enhancesT_N, most likely via enhanced hybridization between the Eu 4fstates and the conduction band, and then, second, causes a structural phase transition that coincides with the conversion of the europium to a fully trivalent state. 

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2. 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)

   Abstract 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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3. 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)

   Abstract 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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4. Structural Stabilization and Piezoelectric Enhancement in Epitaxial (Ti _{1− x} Mg _x ) _0.25 Al _0.75 N(0001) Layers

   https://doi.org/10.1002/adfm.202001915  

   Wang, Baiwei; Aryana, Kiumars; Gaskins, John_T; Hopkins, Patrick_E; Khare, Sanjay_V; Gall, Daniel (June 2020, Advanced Functional Materials)

   Abstract Epitaxial (Ti_1−xMg_x)_0.25Al_0.75N(0001)/Al₂O₃(0001) layers are used as a model system to explore how Fermi‐level engineering facilitates structural stabilization of a host matrix despite the intentional introduction of local bonding instabilities that enhance the piezoelectric response. The destabilizing octahedral bonding preference of Ti dopants and the preferred 0.67 nitrogen‐to‐Mg ratio for Mg dopants deteriorate the wurtzite AlN matrix for both Ti‐rich (x< 0.2) and Mg‐rich (x≥ 0.9) alloys. Conversely,x= 0.5 leads to a stability peak with a minimum in the lattice constant ratioc/a, which is caused by a Fermi‐level shift into the bandgap and a trend toward nondirectional ionic bonding, leading to a maximum in the expected piezoelectric stress constante₃₃. The refractive index and the subgap absorption decrease withx, the optical bandgap increases, and the elastic constant along the hexagonal axisC₃₃= 270 ± 14 GPa remains composition independent, leading to an expected piezoelectric constantd₃₃= 6.4 pC N⁻¹atx= 0.5, which is 50% larger than for the pure AlN matrix. Thus, contrary to the typical anticorrelation between stability and electromechanical coupling, the (Ti_1−xMg_x)_0.25Al_0.75N system exhibits simultaneous maxima in the structural stability and the piezoelectric response atx= 0.5. 

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5. Phase Stability and Thermal Equation of State of Iron Carbide Fe ₃ C to 245 GPa

   https://doi.org/10.1029/2019GL084545  

   Hu, Xiaojun; Fei, Yingwei; Yang, Jing; Cai, Yang; Ye, Shijia; Qi, Meilan; Liu, Fusheng; Zhang, Mingjian (October 2019, Geophysical Research Letters)

   Abstract We conducted shock wave experiments on iron carbide Fe₃C up to a Hugoniot pressure of 245 GPa. The correlation between the particle velocity (u_p) and shock wave velocity (u_s) can be fitted into a linear relationship,u_s= 4.627(±0.073) + 1.614(±0.028)u_p. The density‐pressure relationship is consistent with a single‐phase compression without decomposition. The inference is further supported by the comparison of the observed Hugoniot density with the calculated Hugoniot curves of possible decomposition products. The new Hugoniot data combined with the reported 300‐K isothermal compression data yielded a Grüneisen parameter ofγ= 2.23(7.982/ρ)^0.29. The thermal equation of state of Fe₃C is further used to calculate the density profile of Fe₃C along the Earth's adiabatic geotherm. The density of Fe₃C was found to be too low (by ~5%) to match the observed density in the Earth's inner core, and Fe₃C is unlikely a dominant component of the inner core. 

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