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1. Global perspectives of the bulk electronic structure of URu ₂ Si ₂ from angle-resolved photoemission

   https://doi.org/10.1088/2516-1075/ac4315  

   Denlinger, J. D.; Kang, J-S; Dudy, L.; Allen, J. W.; Kim, Kyoo; Shim, J-H; Haule, K.; Sarrao, J. L.; Butch, N. P.; Maple, M. B. (January 2022, Electronic Structure)

   Abstract Previous high-resolution angle-resolved photoemission (ARPES) studies of URu₂Si₂have characterized the temperature-dependent behavior of narrow-band states close to the Fermi level (E_F) at low photon energies near the zone center, with an emphasis on electronic reconstruction due to Brillouin zone folding. A substantial challenge to a proper description is that these states interact with other hole-band states that are generally absent from bulk-sensitive soft x-ray ARPES measurements. Here we provide a more globalk-space context for the presence of such states and their relation to the bulk Fermi surface (FS) topology using synchrotron-based wide-angle and photon energy-dependent ARPES mapping of the electronic structure using photon energies intermediate between the low-energy regime and the high-energy soft x-ray regime. Small-spot spatial dependence,f-resonant photoemission, Si 2pcore-levels, x-ray polarization, surface-dosing modification, and theoretical surface slab calculations are employed to assist identification of bulk versus surface state character of theE_F-crossing bands and their relation to specific U- or Si-terminations of the cleaved surface. The bulk FS topology is critically compared to density functional theory (DFT) and to dynamical mean field theory calculations. In addition to clarifying some aspects of the previously measured high symmetry Γ,ZandXpoints, incommensurate 0.6a* nested Fermi-edge states located alongZ–N–Zare found to be distinctly different from the DFT FS prediction. The temperature evolution of these states aboveT_HO, combined with a more detailed theoretical investigation of this region, suggests a key role of theN-point in the hidden order transition. 

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2. Evidence of symmetry breaking in a Gd ₂ di-nuclear molecular polymer

   https://doi.org/10.1039/D2CP03050K  

   Ekanayaka, Thilini; Jiang, Tao; Delahaye, Emilie; Perez, Olivier; Sutter, Jean-Pascal; Le, Duy; N'Diaye, Alpha T.; Streubel, Robert; Rahman, Talat S.; Dowben, Peter A. (February 2023, Physical Chemistry Chemical Physics)

   A chiral 3D coordination compound, [Gd 2 (L) 2 (ox) 2 (H 2 O) 2 ], arranged around a dinuclear Gd unit has been characterized by X-ray photoemission and X-ray absorption measurements in the context of density functional theory studies. Core level photoemission of the Gd 5p multiplet splittings indicates that spin orbit coupling dominates over j–J coupling evident in the 5p core level spectra of Gd metal. Indications of spin–orbit coupling are consistent with the absence of inversion symmetry due to the ligand field. Density functional theory predicts antiferromagnet alignment of the Gd 2 dimers and a band gap of the compound consistent with optical absorption. 

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3. LiMo ₈ O ₁₀ : Polar Crystal Structure with Infinite Edge-Sharing Molybdenum Octahedra

   https://doi.org/10.1021/acs.inorgchem.2c01917  

   Messegee, Zachary T.; Gall, Philippe; Bhandari, Hari; Siegfried, Peter E.; Kang, Chang-Jong; Chen, Benjamin; Conti, Carl R.; Chen, Banghao; Croft, Mark; Zhang, Qiang; et al (September 2022, Inorganic Chemistry)

   Polycrystalline LiMo8O10 was prepared in a sealed Mo crucible at 1380 °C for 48 h using the conventional high-temperature solid-state method. The polar tetragonal crystal structure (space group I41md) is confirmed based on the Rietveld refinement of powder neutron diffraction and 7Li/6Li solid-state NMR. The crystal structure features infinite chains of Mo4O5 (i.e., Mo2Mo4/2O6/2O6/3) as a repeat unit containing edge-sharing Mo6 octahedra with strong Mo–Mo metal bonding along the chain. X-ray absorption near-edge spectroscopy of the Mo-L3 edge is consistent with the formal Mo valence/configuration. Magnetic measurements reveal that LiMo8O10 is paramagnetic down to 1.8 K. Temperature-dependent resistivity [ρ(T)] measurement indicates a semiconducting behavior that can be fitted with Mott’s variable range hopping conduction mechanism in the temperature range of 215 and 45 K. The ρ(T) curve exhibits an exponential increase below 5 K with a large ratio of ρ1.8/ρ300 = 435. LiMo8O10 shows a negative field-dependent magnetoresistance between 2 and 25 K. Heat capacity measurement fitted with the modified Debye model yields the Debye temperature of 365 K. 

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4. Effect of Au/HfS ₃ interfacial interactions on properties of HfS ₃ -based devices

   https://doi.org/10.1039/d2cp01254e  

   Dhingra, Archit; Lipatov, Alexey; Loes, Michael J.; Abourahma, Jehad; Pink, Maren; Sinitskii, Alexander; Dowben, Peter A. (June 2022, Physical Chemistry Chemical Physics)

   X-ray photoemission spectroscopy (XPS) has been used to examine the interaction between Au and HfS 3 at the Au/HfS 3 interface. XPS measurements reveal dissociative chemisorption of O 2 , leading to the formation of an oxide of Hf at the surface of HfS 3 . This surface hafnium oxide, along with the weakly chemisorbed molecular species, such as O 2 and H 2 O, are likely responsible for the observed p-type characteristics of HfS 3 reported elsewhere. HfS 3 devices exhibit n-type behaviour if measured in vacuum but turn p-type in air. Au thickness-dependent XPS measurements provide clear evidence of band bending as the S 2p and Hf 4f core-level peak binding energies for Au/HfS 3 are found to be shifted to higher binding energies. This band bending implies formation of a Schottky-barrier at the Au/HfS 3 interface, which explains the low measured charge carrier mobilities of HfS 3 -based devices. The transistor measurements presented herein also indicate the existence of a Schottky barrier, consistent with the XPS core-level binding energy shifts, and show that the bulk of HfS 3 is n-type. 

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5. Probing the unpaired Fe spins across the spin crossover of a coordination polymer

   https://doi.org/10.1039/D0MA00612B  

   Ekanayaka, Thilini K.; Kurz, Hannah; Dale, Ashley S.; Hao, Guanhua; Mosey, Aaron; Mishra, Esha; N’Diaye, Alpha T.; Cheng, Ruihua; Weber, Birgit; Dowben, Peter A. (February 2021, Materials Advances)

   null (Ed.)

   For the spin crossover coordination polymer [Fe(L1)(bipy)] n (where L1 is a N 2 O 2 2− coordinating Schiff base-like ligand bearing a phenazine fluorophore and bipy = 4,4′-bipyridine), there is compelling additional evidence of a spin state transition. Both Fe 2p X-ray absorption and X-ray core level photoemission spectroscopies confirm that a spin crossover takes place, as observed by magnetometry. Yet the details of the temperature dependent changes of the spin state inferred from both X-ray absorption and X-ray core level photoemission, differ from magnetometry, particularly with regard to the apparent critical transition temperatures and the cooperative nature of the curve progression in general. Comparing the experimental spin crossover data to Ising model simulations, a transition activation energy in the region of 160 to 175 meV is indicated, along with a nonzero exchange J . Overall, the implication is that there may be perturbations to the bistability of spin states, that are measurement dependent or that the surface differs from the bulk with regard to the cooperative effects observed upon spin transition. 

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