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1. Room-temperature valence transition in a strain-tuned perovskite oxide

   https://doi.org/10.1038/s41467-022-35024-8  

   Chaturvedi, Vipul; Ghosh, Supriya; Gautreau, Dominique; Postiglione, William M.; Dewey, John E.; Quarterman, Patrick; Balakrishnan, Purnima P.; Kirby, Brian J.; Zhou, Hua; Cheng, Huikai; et al (December 2022, Nature Communications)

   Abstract Cobalt oxides have long been understood to display intriguing phenomena known as spin-state crossovers, where the cobalt ion spin changes vs. temperature, pressure, etc. A very different situation was recently uncovered in praseodymium-containing cobalt oxides, where a first-order coupled spin-state/structural/metal-insulator transition occurs, driven by a remarkable praseodymium valence transition. Such valence transitions, particularly when triggering spin-state and metal-insulator transitions, offer highly appealing functionality, but have thus far been confined to cryogenic temperatures in bulk materials (e.g., 90 K in Pr 1- x Ca x CoO 3 ). Here, we show that in thin films of the complex perovskite (Pr 1- y Y y ) 1- x Ca x CoO 3-δ , heteroepitaxial strain tuning enables stabilization of valence-driven spin-state/structural/metal-insulator transitions to at least 291 K, i.e., around room temperature. The technological implications of this result are accompanied by fundamental prospects, as complete strain control of the electronic ground state is demonstrated, from ferromagnetic metal under tension to nonmagnetic insulator under compression, thereby exposing a potential novel quantum critical point. 

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2. Correlation-driven electronic reconstruction in FeTe1−xSex

   https://doi.org/10.1038/s42005-022-00805-6  

   Huang, Jianwei; Yu, Rong; Xu, Zhijun; Zhu, Jian-Xin; Oh, Ji Seop; Jiang, Qianni; Wang, Meng; Wu, Han; Chen, Tong; Denlinger, Jonathan D.; et al (December 2022, Communications Physics)

   Abstract Electronic correlation is of fundamental importance to high temperature superconductivity. While the low energy electronic states in cuprates are dominantly affected by correlation effects across the phase diagram, observation of correlation-driven changes in fermiology amongst the iron-based superconductors remains rare. Here we present experimental evidence for a correlation-driven reconstruction of the Fermi surface tuned independently by two orthogonal axes of temperature and Se/Te ratio in the iron chalcogenide family FeTe 1− x Se x . We demonstrate that this reconstruction is driven by the de-hybridization of a strongly renormalized d x y orbital with the remaining itinerant iron 3 d orbitals in the emergence of an orbital-selective Mott phase. Our observations are further supported by our theoretical calculations to be salient spectroscopic signatures of such a non-thermal evolution from a strongly correlated metallic phase into an orbital-selective Mott phase in d x y as Se concentration is reduced. 

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3. Origin of the ²⁹ Si NMR chemical shift in R ₃ Si–X and relationship to the formation of silylium (R ₃ Si ⁺ ) ions

   https://doi.org/10.1039/D0DT02099K  

   Huynh, Winn; Conley, Matthew P. (November 2020, Dalton Transactions)

   null (Ed.)

   The origin in deshielding of 29 Si NMR chemical shifts in R 3 Si–X, where X = H, OMe, Cl, OTf, [CH 6 B 11 X 6 ], toluene, and O X (O X = surface oxygen), as well as i Pr 3 Si + and Mes 3 Si + were studied using DFT methods. At the M06-L/6-31G(d,p) level of theory the geometry optimized structures agree well with those obtained experimentally. The trends in 29 Si NMR chemical shift also reproduce experimental trends; i Pr 3 Si–H has the most shielded 29 Si NMR chemical shift and free i Pr 3 Si + or isolable Mes 3 Si + have the most deshielded 29 Si NMR chemical shift. Natural localized molecular orbital (NLMO) analysis of the contributions to paramagnetic shielding ( σ p ) in these compounds shows that Si–R (R = alkyl, H) bonding orbitals are the major contributors to deshielding in this series. The Si–R bonding orbitals are coupled to the empty p-orbital in i Pr 3 Si + or Mes 3 Si + , or to the orbital in R 3 Si–X. This trend also applies to surface bound R 3 Si–O X . This model also explains chemical shift trends in recently isolated t Bu 2 SiH 2 + , t BuSiH 2 + , and SiH 3 + that show more shielded 29 Si NMR signals than R 3 Si + species. There is no correlation between isotropic 29 Si NMR chemical shift and charge at silicon. 

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4. Emergent Epitaxial Configuration of Pr ₃ IrO ₇ Domains via YSZ (111) Substrate

   https://doi.org/10.1002/sstr.202500005  

   Noh, Gahee; Guo, Lu; Pal, Pratap; Campbell, Neil; Rzchowski, Mark Steven; Eom, Chang‐Beom; Choi, Si‐Young (August 2025, Small Structures)

   The 5drare Earth iridate is an intriguing material with exhibiting exotic electronic and magnetic phases due to spin‐orbit coupled states. Ternary iridium oxidesLn₃IrO₇contain an unusual Ir⁵⁺(5d⁴) system, which remain a subject of active research. Fabricating epitaxialLn₃IrO₇films is challenging due to substrate compatibility, but it offers a valuable platform to explore electronic and magnetic behaviors under reduced dimensionality and substrate interactions, revealing novel phenomena based on Ir⁵⁺(5d⁴). In this regard, this demonstrates that Pr₃IrO₇with its highly anisotropic orthorhombic structure can be epitaxially grown on a cubic (111)‐oriented yttrium‐stabilized ZrO₂(YSZ) substrate. Pr₃IrO₇film exhibits six epitaxial domains, where the (220) and (202) planes aligning epitaxially to YSZ (111) with the threefold symmetry. This diverse domain configuration in Pr₃IrO₇film leads to unique magnetic properties, exhibiting spin‐glass‐like behavior. Pr₃IrO₇thin film offers a platform for exploring unconventional magnetic states, and their successful heteroepitaxy on YSZ substrates opens new avenues for discovering novel physical phenomena. 

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5. Valence, charge transfer, and orbital-dependent correlation in bilayer nickelates ${\mathrm{Nd}}_3{\mathrm{Ni}}_2{\mathrm{O}}_7$

   https://doi.org/10.1103/PhysRevB.111.165101  

   Takegami, Daisuke; Okauchi, Takaki; Morales, Edgar Abarca; Fujinuma, Koto; Furo, Mizuki; Yoshimura, Masato; Tsuei, Ku-Ding; Pan, Grace A; Segedin, Dan Ferenc; Song, Qi; et al (April 2025, Physical Review B)

   We examine the bulk electronic structure of ${\mathrm{Nd}}_3{\mathrm{Ni}}_2{\mathrm{O}}_7$using Ni $2p$core-level hard x-ray photoemission spectroscopy combined with density functional theory $+$dynamical mean-field theory. Our results reveal a large deviation of the Ni $3d$occupation from the formal ${\mathrm{Ni}}^{2.5+}$valency, highlighting the importance of the charge transfer from oxygen ligands. We find that the dominant $d^8$configuration is accompanied by nearly equal contributions from $d^7$and $d^9$states, exhibiting an unusual valence state among Ni-based oxides. Finally, we discuss the Ni $d_{x^2-y^2}$and $d_{z^2}$orbital-dependent hybridization, correlation and local spin dynamics. Published by the American Physical Society2025 

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