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1. Spin-orbital Jahn-Teller bipolarons

   https://doi.org/10.1038/s41467-024-46621-0  

   Celiberti, Lorenzo; Fiore_Mosca, Dario; Allodi, Giuseppe; Pourovskii, Leonid V; Tassetti, Anna; Forino, Paola Caterina; Cong, Rong; Garcia, Erick; Tran, Phuong M; De_Renzi, Roberto; et al (December 2024, Nature Communications)

   Abstract Polarons and spin-orbit (SO) coupling are distinct quantum effects that play a critical role in charge transport and spin-orbitronics. Polarons originate from strong electron-phonon interaction and are ubiquitous in polarizable materials featuring electron localization, in particular 3d transition metal oxides (TMOs). On the other hand, the relativistic coupling between the spin and orbital angular momentum is notable in lattices with heavy atoms and develops in 5d TMOs, where electrons are spatially delocalized. Here we combine ab initio calculations and magnetic measurements to show that these two seemingly mutually exclusive interactions are entangled in the electron-doped SO-coupled Mott insulator Ba₂Na_1−xCa_xOsO₆(0 < x < 1), unveiling the formation ofspin-orbital bipolarons. Polaron charge trapping, favoured by the Jahn-Teller lattice activity, converts the Os 5d¹spin-orbital J_eff = 3/2 levels, characteristic of the parent compound Ba₂NaOsO₆(BNOO), into a bipolaron 5d²J_eff = 2 manifold, leading to the coexistence of different J-effective states in a single-phase material. The gradual increase of bipolarons with increasing doping creates robust in-gap states that prevents the transition to a metal phase even at ultrahigh doping, thus preserving the Mott gap across the entire doping range from d¹BNOO to d²Ba₂CaOsO₆(BCOO). 

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2. Emergent charge order near the doping-induced Mott-insulating quantum phase transition in Sr3Ru2O7

   https://doi.org/10.1038/s42005-019-0138-4  

   Leshen, Justin; Kavai, Mariam; Giannakis, Ioannis; Kaneko, Yoshio; Tokura, Yoshi; Mukherjee, Shantanu; Lee, Wei-Cheng; Aynajian, Pegor (March 2019, Communications Physics)

   Abstract Search for novel electronically ordered states of matter emerging near quantum phase transitions is an intriguing frontier of condensed matter physics. In ruthenates, the interplay between Coulomb correlations among the 4delectronic states and their spin-orbit interactions, lead to complex forms of electronic phenomena. Here we investigate the double layered Sr₃(Ru_1−xMn_x)₂O₇and its doping-induced quantum phase transition from a metal to an antiferromagnetic Mott insulator. Using spectroscopic imaging with the scanning tunneling microscope, we visualize the evolution of the electronic states in real- and momentum-space. We find a partial-gap at the Fermi energy that develops with doping to form a weak Mott insulating state. Near the quantum phase transition, we discover a spatial electronic reorganization into a commensurate checkerboard charge order. These findings bear a resemblance to the universal charge order in the pseudogap phase of cuprates and demonstrate the ubiquity of charge order that emanates from doped Mott insulators. 

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3. Mapping Acid–Base Sites on Anatase Titania (100) and (101) Surfaces by Density Functional Theory: The Link Between Lewis Acidity and the Surface Ability to Flex

   https://doi.org/10.3390/surfaces7040070  

   Ignatchenko, Alexey V; Denman, Paige E (December 2024, Surfaces)

   The acidity of anatase titania before and after KOH doping was probed by pyridine adsorption in a pulse microreactor and modeled by DFT optimization of the geometry of CO and pyridine adsorption on a periodic slab of (101) and (100) surfaces using a GGA/PBE functional and verified by an example of a single-point calculation of the optimized geometry using an HSE-06 hybrid functional. The anatase (101) surface was slightly more acidic compared to the (100) surface. Both experimental and computational methods show that the acidity of anatase surfaces decreased after KOH doping and increased after the dissociative adsorption of water. Higher acidity of Ti metal centers was indicated by the shortening of the Ti-N, Ti-C, and C-O bond lengths, increasing the IR frequency of CO and pyridine ring vibrations and energy of adsorption. The DFT calculated energy of pyridine adsorption was analyzed in terms of binding energy and the energy of lattice distortion. The latter was used to construct Hammett plots for the adsorption of 4-substituted pyridines with electron-donating and -withdrawing substituents. The Hammett rho constant was obtained and used to characterize the acidity of various metal centers of −1.51 vs. −1.46 on pristine (101) and (100) surfaces, which were lowered to −1.07 and −1.19 values on KOH-doped (101) and (100) surfaces, respectively. The mechanism of lowering surface acidity via KOH doping proceeds through the stabilization of the atomic structure of Lewis acid centers. When an alkaline metal cation binds to several lattice oxygen atoms, the surface structure becomes more rigid. The ability of Ti atoms to move toward the adsorbate is restricted. Consequently, the lattice distortion energy and binding energy are decreased. In contrast, higher flexibility of the outermost layer of Ti atoms as a result of electron density redistribution, for example, in the presence of water on the surface, allows them to move farther outward, make shorter contacts with the adsorbate, and attain higher energies of binding and lattice distortion. 

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4. Nanoscale visualization and spectral fingerprints of the charge order in ScV6Sn6 distinct from other kagome metals

   https://doi.org/10.1038/s41535-024-00623-9  

   Cheng, Siyu; Ren, Zheng; Li, Hong; Oh, Ji Seop; Tan, Hengxin; Pokharel, Ganesh; DeStefano, Jonathan M.; Rosenberg, Elliott; Guo, Yucheng; Zhang, Yichen; et al (January 2024, npj Quantum Materials)

   Abstract Charge density waves (CDWs) in kagome metals have been tied to many exotic phenomena. Here, using spectroscopic-imaging scanning tunneling microscopy and angle-resolved photoemission spectroscopy, we study the charge order in kagome metal ScV₆Sn₆. The similarity of electronic band structures of ScV₆Sn₆and TbV₆Sn₆(where charge ordering is absent) suggests that charge ordering in ScV₆Sn₆is unlikely to be primarily driven by Fermi surface nesting of the Van Hove singularities. In contrast to the CDW state of cousin kagome metals, we find no evidence supporting rotation symmetry breaking. Differential conductance dI/dVspectra show a partial gapΔ¹_CO ≈ 20 meV at the Fermi level. Interestingly, dI/dVmaps reveal that charge modulations exhibit an abrupt phase shift as a function of energy at energy much higher thanΔ¹_CO, which we attribute to another spectral gap. Our experiments reveal a distinctive nature of the charge order in ScV₆Sn₆with fundamental differences compared to other kagome metals. 

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5. Emergent chirality in a polar meron to skyrmion phase transition

   https://doi.org/10.1038/s41467-023-36950-x  

   Shao, Yu-Tsun; Das, Sujit; Hong, Zijian; Xu, Ruijuan; Chandrika, Swathi; Gómez-Ortiz, Fernando; García-Fernández, Pablo; Chen, Long-Qing; Hwang, Harold Y.; Junquera, Javier; et al (March 2023, Nature Communications)

   Abstract Polar skyrmions are predicted to emerge from the interplay of elastic, electrostatic and gradient energies, in contrast to the key role of the anti-symmetric Dzyalozhinskii-Moriya interaction in magnetic skyrmions. Here, we explore the reversible transition from a skyrmion state (topological charge of −1) to a two-dimensional, tetratic lattice of merons (with topological charge of −1/2) upon varying the temperature and elastic boundary conditions in [(PbTiO₃)₁₆/(SrTiO₃)₁₆]₈membranes. This topological phase transition is accompanied by a change in chirality, from zero-net chirality (in meronic phase) to net-handedness (in skyrmionic phase). We show how scanning electron diffraction provides a robust measure of the local polarization simultaneously with the strain state at sub-nm resolution, while also directly mapping the chirality of each skyrmion. Using this, we demonstrate strain as a crucial order parameter to drive isotropic-to-anisotropic structural transitions of chiral polar skyrmions to non-chiral merons, validated with X-ray reciprocal space mapping and phase-field simulations. 

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