Articles de revues : « 3d Transition Metal Oxides »

1

Seike, Tetsuya, et Junichi Nagai. « Electrochromism of 3d transition metal oxides ». Solar Energy Materials 22, n^o 2-3 (juillet 1991) : 107–17. http://dx.doi.org/10.1016/0165-1633(91)90010-i.

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Krivanek, Ondrej L., et James H. Paterson. « Elnes of 3d transition-metal oxides ». Ultramicroscopy 32, n^o 4 (mai 1990) : 313–18. http://dx.doi.org/10.1016/0304-3991(90)90077-y.

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Paterson, James H., et Ondrej L. Krivanek. « Elnes of 3d transition-metal oxides ». Ultramicroscopy 32, n^o 4 (mai 1990) : 319–25. http://dx.doi.org/10.1016/0304-3991(90)90078-z.

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4

Tokura, Y. « Metal-insulator phenomena in 3d transition metal oxides ». Physica C : Superconductivity 235-240 (décembre 1994) : 138–41. http://dx.doi.org/10.1016/0921-4534(94)91332-3.

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Merer, A. J. « Spectroscopy of the Diatomic 3d Transition Metal Oxides ». Annual Review of Physical Chemistry 40, n^o 1 (octobre 1989) : 407–38. http://dx.doi.org/10.1146/annurev.pc.40.100189.002203.

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Zimmermann, R., P. Steiner, R. Claessen, F. Reinert et S. Hüfner. « Electronic structure systematics of 3d transition metal oxides ». Journal of Electron Spectroscopy and Related Phenomena 96, n^o 1-3 (novembre 1998) : 179–86. http://dx.doi.org/10.1016/s0368-2048(98)00234-5.

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7

Terauchi, Masami. « Information of valence charge of 3d transition metal elements observed in L-emission spectra ». Microscopy 68, n^o 4 (14 mai 2019) : 330–37. http://dx.doi.org/10.1093/jmicro/dfz020.

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Abstract L-emission spectra of 3d transition metal elements from Sc to Zn and some oxides were measured to examine the relation between L-emission intensities of Lα, Lβ, Lℓ, and Lη and valences of those elements by using a soft X-ray emission spectrometer attached to a scanning electron microscope. Lα,β emission intensity due to transitions from valence bands to core 2p levels compared with Lℓ,η emission intensity due to transitions from core 3 s to deeper 2p levels, Lα,β/Lℓ,η was found to be a key parameter. A linear relation was found between the number of 3d electrons and the intensity ratio of Lα,β/(Lα,β+ Lℓ,η) from Sc to Ni, except for Cr. It takes into account not only a change in N3d but also a change of transition probability due to a change in N3d In the case of 3d metal oxides, the evaluation based on the equation showed an overestimation of the calculated number of 3d electrons, which could be due to a charge transfer from ligand oxygen atoms to the transition metal element, resulting from a core-hole effect in the intermediate state.

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SEIKE, Tetsuya, et Junichi NAGAI. « Electrochromism in thin films of 3d transition metal oxides. » Hyomen Kagaku 10, n^o 5 (1989) : 314–19. http://dx.doi.org/10.1380/jsssj.10.314.

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Eisaki, H., T. Ido, K. Magoshi, M. Mochizuki, H. Yamatsu, T. Ito et S. Uchida. « Metal-insulator transition in 3d transition-metal oxides with ABO3 and A2BO4 type structures ». Physica C : Superconductivity 185-189 (décembre 1991) : 1295–96. http://dx.doi.org/10.1016/0921-4534(91)91871-z.

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Azuma, Masaki, Yuki Sakai, Takumi Nishikubo, Masaichiro Mizumaki, Tetsu Watanuki, Takashi Mizokawa, Kengo Oka, Hajime Hojo et Makoto Naka. « Systematic charge distribution changes in Bi- and Pb-3d transition metal perovskites ». Dalton Transactions 47, n^o 5 (2018) : 1371–77. http://dx.doi.org/10.1039/c7dt03244g.

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Charge distribution changes in Bi- and Pb-3d transition metal perovskite type oxides were examined. The change in the depth of the d level of the transition metal causes the intermetallic charge transfer.

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Long, Xinghui, Pengfei Yu, Nian Zhang, Chun Li, Xuefei Feng, Guoxi Ren, Shun Zheng, Jiamin Fu, Fangyi Cheng et Xiaosong Liu. « Direct Spectroscopy for Probing the Critical Role of Partial Covalency in Oxygen Reduction Reaction for Cobalt-Manganese Spinel Oxides ». Nanomaterials 9, n^o 4 (9 avril 2019) : 577. http://dx.doi.org/10.3390/nano9040577.

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Nanocrystalline multivalent metal spinels are considered as attractive non-precious oxygen electrocatalysts. Identifying their active sites and understanding their reaction mechanisms are essential to explore novel transition metal (TM) oxides catalysts and further promote their catalytic efficiency. Here we report a systematic investigation, by means of soft X-ray absorption spectroscopy (sXAS), on cubic and tetragonal CoxMn3-xO4 (x = 1, 1.5, 2) spinel oxides as a family of highly active catalysts for the oxygen reduction reaction (ORR). We demonstrate that the ORR activity for oxide catalysts primarily correlates to the partial covalency of between O 2p orbital with Mn4+ 3d t2g-down/eg-up, Mn3+ 3d eg-up and Co3+ 3d eg-up orbitals in octahedron, which is directly revealed by the O K-edge sXAS. Our findings propose the critical influences of the partial covalency between oxygen 2p band and specific metal 3d band on the competition between intermediates displacement of the ORR, and thus highlight the importance of electronic structure in controlling oxide catalytic activity.

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Tejaswini, G., P. Lakshmi Kishore, V. Naga Lakshmi et K. Bhagya Lakshmi. « A Comprehensive Review on Green Synthetic Approaches and Applications of 3d-Series Metal Oxide Nanoparticles ». Asian Journal of Chemistry 34, n^o 10 (2022) : 2478–88. http://dx.doi.org/10.14233/ajchem.2022.23904.

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Transition metal oxides have been studied by many workers of fields who want to find new ways to use them in medical devices and other fields. Researchers have done a lot of research on solid-state synthesis methods, which require high temperatures and make molecules that are thermodynamically stable. Transition metal oxides have been used for a wide range of things, from nanoparticles that deliver drugs to systems that store information in more than one state. In materials science and technology research and development, a new era of “green synthesis” methods is getting a great attention. Basically, green synthesis of materials and nanomaterials, which is done through a process of regulation, control, cleaning and remediation, will directly help make them more friendly to the environment. In this review, various green approaches for 3d-series metal oxide nanoparticles and their applications are discussed.

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Kim, Hyo-Young, Jeeyoung Shin, Il-Chan Jang et Young-Wan Ju. « Hydrothermal Synthesis of Three-Dimensional Perovskite NiMnO3 Oxide and Application in Supercapacitor Electrode ». Energies 13, n^o 1 (19 décembre 2019) : 36. http://dx.doi.org/10.3390/en13010036.

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Supercapacitors are attractive as a major energy storage device due to their high coulombic efficiency and semi-permanent life cycle. Transition metal oxides are used as electrode material in supercapacitors due to their high conductivity, capacitance, and multiple oxidation states. Nanopowder transition metal oxides exhibit low specific surface area, ion diffusion, electrical conductivity, and structural stability compared with the three-dimensional (3D) structure. Furthermore, unstable performance during long-term testing can occur via structural transition. Therefore, it is necessary to synthesize a transition metal oxide with a high specific surface area and a stable structure for supercapacitor application. Transition metal oxides with a perovskite structure control structural transition and improve conductivity. In this study, a NiMnO3 perovskite oxide with a high specific surface area and electrochemical properties was obtained via hydrothermal synthesis at low temperature. Hydrothermal synthesis was used to fabricate materials with an aqueous solution under high temperature and pressure. The shape and composition were regulated by controlling the hydrothermal synthesis reaction temperature and time. The synthesis of NiMnO3 was controlled by the reaction time to alter the specific surface area and morphology. The prepared perovskite NiMnO3 oxide with a three-dimensional structure can be used as an active electrode material for supercapacitors and electrochemical catalysts. The prepared NiMnO3 perovskite oxide showed a high specific capacitance of 99.03 F·g−1 and excellent cycle stability with a coulombic efficiency of 77% even after 7000 cycles.

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Mitchell, James B., Ruocun Wang, Jesse S. Ko, Jeffrey W. Long et Veronica Augustyn. « Critical Role of Structural Water for Enhanced Li⁺ Insertion Kinetics in Crystalline Tungsten Oxides ». Journal of The Electrochemical Society 169, n^o 3 (1 mars 2022) : 030534. http://dx.doi.org/10.1149/1945-7111/ac58c8.

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Electrochemical ion insertion into transition metal oxides forms the foundation of several energy technologies. Transition metal oxides can exhibit sluggish ion transport and/or phase-transformation kinetics during ion insertion that can limit their performance at high rates (<10 min). In this study, we investigate the role of structural water in transition metal oxides during Li+ insertion using staircase potentiostatic electrochemical impedance spectroscopy (SPEIS) and electrochemical quartz crystal microbalance (EQCM) analysis of WO3·H2O and WO3 thin-film electrodes. Overall, the presence of structural water in WO3·H2O improves Li+ insertion kinetics compared to WO3 and leads to a less potential-dependent insertion process. Operando electrogravimetry and 3D Bode impedance analyses of nanostructured films reveal that the presence of structural water promotes charge accommodation without significant co-insertion of solvent, leading to our hypothesis that the electrochemically induced structural transitions of WO3 hinder the electrode response at faster timescales (<10 min). Designing layered materials with confined fluids that exhibit less structural transitions may lead to more versatile ion-insertion hosts for next-generation electrochemical technologies.

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Lu, Xuanming, Kazuyoshi Kanamori et Kazuki Nakanishi. « Hierarchically porous monoliths based on low-valence transition metal (Cu, Co, Mn) oxides : gelation and phase separation ». National Science Review 7, n^o 11 (27 mai 2020) : 1656–66. http://dx.doi.org/10.1093/nsr/nwaa103.

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Abstract Hierarchically porous monoliths based on copper (Cu), cobalt (Co) and manganese (Mn) oxides with three-dimensionally (3D) interconnected macropores and open nanopores were prepared using metal bromides as precursors via a sol–gel process accompanied by phase separation. The difficulty of gelation for low-valence metal cation was overcome by introducing a highly electronegative Br atom near to the metal atom to control the rates of hydrolysis and polycondensation. The 3D interconnected macropores were obtained using appropriate polymers to induce phase separation. The domain sizes of macropores and skeletons can be controlled by reaction parameters such as concentration and/or average molecular weight of polymers, and the amount of hydrochloric acid. The crystalline metal oxide monoliths with their 3D interconnected macroporous structure preserved were obtained after heat treatment in air.

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Patzke, Greta R., et Michael Binnewies. « Chemischer Transport fester Lösungen am Beispiel von Mischspineilen / Chemical Transport of Solid Solutions : Mixed Spinels ». Zeitschrift für Naturforschung B 55, n^o 1 (1 janvier 2000) : 26–34. http://dx.doi.org/10.1515/znb-2000-0106.

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Chemical vapor transport is a suitable pathway to controllable syntheses of mixed spinel systems. Solid solutions of spinels on the basis of 3d transition metal oxides and gallium oxide can be prepared using various transport agents (TeCl4, Cl2, HCl). Transport processes observed are consistent with theoretical predictions

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Parida, Priyadarshini, Ravi Kashikar, Ajit Jena et B. R. K. Nanda. « Universality in the electronic structure of 3d transition metal oxides ». Journal of Physics and Chemistry of Solids 123 (décembre 2018) : 133–49. http://dx.doi.org/10.1016/j.jpcs.2018.04.009.

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Sugiyama, J., H. Nozaki, I. Umegaki, W. Higemoto, E. J. Ansaldo, J. H. Brewer, H. Sakurai, T.-H. Kao, H.-D. Yang et M. Månsson. « Microscopic magnetic nature of K2NiF4-type 3d transition metal oxides ». Journal of Physics : Conference Series 551 (16 décembre 2014) : 012011. http://dx.doi.org/10.1088/1742-6596/551/1/012011.

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Meer, H., O. Gomonay, A. Wittmann et M. Kläui. « Antiferromagnetic insulatronics : Spintronics in insulating 3d metal oxides with antiferromagnetic coupling ». Applied Physics Letters 122, n^o 8 (20 février 2023) : 080502. http://dx.doi.org/10.1063/5.0135079.

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Antiferromagnetic transition metal oxides are an established and widely studied materials system in the context of spin-based electronics, commonly used as passive elements in exchange bias-based memory devices. Currently, major interest has resurged due to the recent observation of long-distance spin transport, current-induced switching, and THz emission. As a result, insulating transition metal oxides are now considered to be attractive candidates for active elements in future spintronic devices. Here, we discuss some of the most promising materials systems and highlight recent advances in reading and writing antiferromagnetic ordering. This article aims to provide an overview of the current research and potential future directions in the field of antiferromagnetic insulatronics.

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Tanaka, Arata, et Takeo Jo. « Resonant 3d, 3pand 3sPhotoemission in Transition Metal Oxides Predicted at 2pThreshold ». Journal of the Physical Society of Japan 63, n^o 7 (15 juillet 1994) : 2788–807. http://dx.doi.org/10.1143/jpsj.63.2788.

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Chen, Huixin, Qiaobao Zhang, Xiang Han, Junjie Cai, Meilin Liu, Yong Yang et Kaili Zhang. « 3D hierarchically porous zinc–nickel–cobalt oxide nanosheets grown on Ni foam as binder-free electrodes for electrochemical energy storage ». Journal of Materials Chemistry A 3, n^o 47 (2015) : 24022–32. http://dx.doi.org/10.1039/c5ta07258a.

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3D hierarchically porous transition metal oxides, particularly those involving different metal ions of mixed valence states and constructed from interconnected nano-building blocks directly grown on conductive current collectors, are promising electrode candidates for energy storage devices such as Li-ion batteries and supercapacitors.

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Dobrodey, N. V., et Yu V. Luniakov. « Intensities of electric quadrupole transitions in the x-ray spectra of transition 3d-metal oxides ». Physica Scripta 50, n^o 1 (1 juillet 1994) : 19–24. http://dx.doi.org/10.1088/0031-8949/50/1/003.

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Abdelwahab, Abdalla, Francisco Carrasco-Marín et Agustín F. Pérez-Cadenas. « Binary and Ternary 3D Nanobundles Metal Oxides Functionalized Carbon Xerogels as Electrocatalysts toward Oxygen Reduction Reaction ». Materials 13, n^o 16 (10 août 2020) : 3531. http://dx.doi.org/10.3390/ma13163531.

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A series of carbon xerogels doped with cobalt, nickel, and iron have been prepared through the sol–gel method. The doped carbon xerogels were further functionalized with binary and ternary transition metal oxides containing Co, Ni, and Zn oxides by the hydrothermal method. A development in the mesopore volume is achieved for functionalized carbon xerogel doped with iron. However, in the functionalization of carbon xerogel with ternary metal oxides, a reduction in pore diameter and mesopore volume is found. In addition, all functionalized metal oxides/carbon are in the form of 3D nanobundles with different lengths and widths. The prepared samples have been tested as electrocatalysts for oxygen reduction reaction (ORR) in basic medium. All composites showed excellent oxygen reduction reaction activity; the low equivalent series resistance of the Zn–Ni–Co/Co–CX composite was especially remarkable, indicating high electronic conductivity. It has been established that the role of Zn in this type of metal oxides nanobundles-based ORR catalyst is not only positive, but its effect could be enhanced by the presence of Ni.

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Khrussanova, M., M. Terzieva, P. Peshev, I. Konstanchuk et E. Ivanov. « Hydriding Kinetics of Mixtures Containing Some 3d-Transition Metal Oxides and Magnesium* ». Zeitschrift für Physikalische Chemie 164, Part_2 (janvier 1989) : 1261–66. http://dx.doi.org/10.1524/zpch.1989.164.part_2.1261.

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Tian, Weiliang, Haoyuan Li, Bangchang Qin, Yuqi Xu, Yongchao Hao, Yaping Li, Guoxin Zhang, Junfeng Liu, Xiaoming Sun et Xue Duan. « Tuning the wettability of carbon nanotube arrays for efficient bifunctional catalysts and Zn–air batteries ». Journal of Materials Chemistry A 5, n^o 15 (2017) : 7103–10. http://dx.doi.org/10.1039/c6ta10505j.

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The wettability of 3D carbon nanotube arrays (CNTAs) was tuned by controlling the nitrogen doping degree, and superhydrophilic nitrogen-doped CNTAs were obtained for anchoring transition metal oxides as bifunctional non-Pt electrocatalysts for high-performance zinc–air batteries.

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Nakai, Shun-ichi, Tsutomu Mitsuishi, Hidenao Sugawara, Hideki Maezawa, Tokuo Matsukawa, Shichiro Mitani, Kazuo Yamasaki et Takashi Fujikawa. « OxygenKx-ray-absorption near-edge structure of alkaline-earth-metal and 3d-transition-metal oxides ». Physical Review B 36, n^o 17 (15 décembre 1987) : 9241–46. http://dx.doi.org/10.1103/physrevb.36.9241.

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Mitchell, James B., Matthew Chagnot et Veronica Augustyn. « Hydrous Transition Metal Oxides for Electrochemical Energy and Environmental Applications ». Annual Review of Materials Research 53, n^o 1 (3 juillet 2023) : 1–23. http://dx.doi.org/10.1146/annurev-matsci-080819-124955.

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Hydrous transition metal oxides (TMOs) are redox-active materials that confine structural water within their bulk, organized in 1D, 2D, or 3D networks. In an electrochemical cell, hydrous TMOs can interact with electrolyte species not only via their outer surface but also via their hydrous inner surface, which can transport electrolyte species to the interior of the material. Many TMOs operating in an aqueous electrochemical environment transform to hydrous TMOs, which then serve as the electrochemically active phase. This review summarizes the physicochemical properties of hydrous TMOs and recent mechanistic insights into their behavior in electrochemical reactions of interest for energy storage, conversion, and environmental applications. Particular focus is placed on first-principles calculations and operando characterization to obtain an atomistic view of their electrochemical mechanisms. Hydrous TMOs represent an important class of energy and environmental materials in aqueous and nonaqueous environments. Further understanding of their interaction with electrolyte species is likely to yield advancements in electrochemical reactivity and kinetics for energy and environmental applications.

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Stroud, R. M., et J. H. Scott. « Valence Mapping of Particulate 3D-Transition Metal Oxides Using Energyfiltered Transmission Electron Microscopy ». Microscopy and Microanalysis 6, S2 (août 2000) : 176–77. http://dx.doi.org/10.1017/s1431927600033377.

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Particulate, mixed-valence transition metal oxides are frequently used for battery, catalytic and magnetic applications. For example, the Li ion exchange battery exploits charge transfer of mixed Mn+3, Mn+4 materials. Charge localization and phase separation, especially at particle surfaces, are critical issues for determining the materials’ useful properties, be it catalytic activity or saturation magnetization. The ability to image the charge localization and correlate this with crystallographic information would be extremely useful in the study of this class of materials. Using energy-filtered transmission electron microscopy (EFTEM), valence maps of Mn and Co with a ∼ 2 nm scale have been obtained for bulk samples. In principal this technique can de directly extended to the case of particulate samples, however there are some additional experimental challenges, such as thickness and edge effects, that must be addressed. We demonstrate here the feasibility of valence mapping of particulate samples, and discuss the factors that limit quantitative data extraction from the maps.

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Subías, G., J. García, J. Blasco, J. Herrero-Martín et M. C. Sánchez. « Resonant x-ray scattering in 3d-transition-metal oxides : Anisotropy and charge orderings ». Journal of Physics : Conference Series 190 (1 novembre 2009) : 012085. http://dx.doi.org/10.1088/1742-6596/190/1/012085.

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Zimmermann, R., P. Steiner, R. Claessen, F. Reinert, S. Hüfner, P. Blaha et P. Dufek. « Electronic structure of 3d-transition-metal oxides : on-site Coulomb repulsion versus covalency ». Journal of Physics : Condensed Matter 11, n^o 7 (1 janvier 1999) : 1657–82. http://dx.doi.org/10.1088/0953-8984/11/7/002.

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Ramadan, R. M., A. M. Abdelghany et H. A. ElBatal. « Gamma rays Interactions with Bismuth Phosphate Glasses Doped with 3d Transition Metal Oxides ». Silicon 10, n^o 3 (27 mai 2017) : 891–99. http://dx.doi.org/10.1007/s12633-016-9545-2.

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Trujillo-González, Daniel E., María C. Ramírez-Romero, Juan I. Rodríguez et Emilbus A. Uribe. « A DFT-chemotopological study on the 3D transition metal oxides and dioxygen complexes ». Chemical Physics Letters 649 (avril 2016) : 103–10. http://dx.doi.org/10.1016/j.cplett.2016.02.025.

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Benko, F. A., et F. P. Koffyberg. « The optical bandgap and band-edge positions of semiconducting p-type CuYO2 ». Canadian Journal of Physics 63, n^o 10 (1 octobre 1985) : 1306–8. http://dx.doi.org/10.1139/p85-215.

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CuYO2, doped with calcium, is a low-mobility p-type semiconductor. From photoelectrochemical measurements it is found that the valence band edge is 5.3 eV below the vacuum level, typical for oxides with a metal-3d valence band. The lowest bandgap is 1.20 eV and the transition is indirectly allowed. An optical transition at 3.60 eV indicates an oxygen-2p valence band at 7.7 eV below vacuum. The results are discussed with the help of a simplified band scheme.

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Sun, Yu, Qiao Wang, Zhibin Geng, Zhongyuan Liu et Rusen Yang. « Fabrication of two-dimensional 3d transition metal oxides through template assisted cations hydrolysis method ». Chemical Engineering Journal 415 (juillet 2021) : 129044. http://dx.doi.org/10.1016/j.cej.2021.129044.

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Ye, Yifan, Mukes Kapilashrami, Cheng-Hao Chuang, Yi-sheng Liu, Per-Anders Glans et Jinghua Guo. « X-ray spectroscopies studies of the 3d transition metal oxides and applications of photocatalysis ». MRS Communications 7, n^o 1 (8 février 2017) : 53–66. http://dx.doi.org/10.1557/mrc.2017.6.

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Crocombette, J. P., et F. Jollet. « Covalency effect on cation 2p x-ray absorption spectroscopy in 3d transition-metal oxides ». Journal of Physics : Condensed Matter 8, n^o 28 (8 juillet 1996) : 5253–68. http://dx.doi.org/10.1088/0953-8984/8/28/009.

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Tanaka, Arata, et Takeo Jo. « Resonant 3d, 3p and 3s Photoemission in Transition Metal Oxides Predicted at 2p Threshold ». Journal of the Physical Society of Japan 64, n^o 6 (15 juin 1995) : 2248A. http://dx.doi.org/10.1143/jpsj.64.2248a.

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Ogasawara, H., et A. Kotani. « Calculation of electron-energy-loss spectra for 3s → 3d excitation in transition metal oxides ». Journal of Electron Spectroscopy and Related Phenomena 88-91 (mars 1998) : 261–66. http://dx.doi.org/10.1016/s0368-2048(97)00137-0.

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TERZIEVA, M., M. KHRUSSANOVA et P. PESHEV. « Dehydriding kinetics of mechanically alloyed mixtures of magnesium with some 3d transition metal oxides ». International Journal of Hydrogen Energy 16, n^o 4 (1991) : 265–70. http://dx.doi.org/10.1016/0360-3199(91)90019-f.

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Galakhov, V. R., S. M. Butorin, E. Z. Kurmaev et M. A. Korotin. « X-ray emission spectra and valence band structure of the 3d transition metal oxides ». Physica B : Condensed Matter 168, n^o 3 (mars 1991) : 163–69. http://dx.doi.org/10.1016/0921-4526(91)90666-3.

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Suzuki, Chikashi, Jun Kawai, Hirohiko Adachi et Takeshi Mukoyama. « Electronic structures of 3d transition metal (Ti–Cu) oxides probed by a core hole ». Chemical Physics 247, n^o 3 (septembre 1999) : 453–70. http://dx.doi.org/10.1016/s0301-0104(99)00212-8.

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Mehandjiev, D., E. Zhecheva et S. Angelov. « On the possibility of formation of 3d-transition metal mixed oxides with spinel structure ». Thermochimica Acta 95, n^o 1 (novembre 1985) : 155–58. http://dx.doi.org/10.1016/0040-6031(85)80044-7.

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Streltsov, Sergey V., et Daniel I. Khomskii. « Covalent bonds against magnetism in transition metal compounds ». Proceedings of the National Academy of Sciences 113, n^o 38 (6 septembre 2016) : 10491–96. http://dx.doi.org/10.1073/pnas.1606367113.

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Magnetism in transition metal compounds is usually considered starting from a description of isolated ions, as exact as possible, and treating their (exchange) interaction at a later stage. We show that this standard approach may break down in many cases, especially in 4d and 5d compounds. We argue that there is an important intersite effect—an orbital-selective formation of covalent metal–metal bonds that leads to an “exclusion” of corresponding electrons from the magnetic subsystem, and thus strongly affects magnetic properties of the system. This effect is especially prominent for noninteger electron number, when it results in suppression of the famous double exchange, the main mechanism of ferromagnetism in transition metal compounds. We study this mechanism analytically and numerically and show that it explains magnetic properties of not only several 4d–5d materials, including Nb2O2F3 and Ba5AlIr2O11, but can also be operative in 3d transition metal oxides, e.g., in CrO2 under pressure. We also discuss the role of spin–orbit coupling on the competition between covalency and magnetism. Our results demonstrate that strong intersite coupling may invalidate the standard single-site starting point for considering magnetism, and can lead to a qualitatively new behavior.

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Williams, A. J., B. M. Sobotka et J. P. Attfield. « Charge disorder effects in 3d transition metal oxide perovskites ». Journal of Solid State Chemistry 173, n^o 2 (juillet 2003) : 456–61. http://dx.doi.org/10.1016/s0022-4596(03)00012-4.

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Kronawitter, Coleman X., Jonathan R. Bakke, Damon A. Wheeler, Wei-Cheng Wang, Chinglin Chang, Bonnie R. Antoun, Jin Z. Zhang et al. « Electron Enrichment in 3d Transition Metal Oxide Hetero-Nanostructures ». Nano Letters 11, n^o 9 (14 septembre 2011) : 3855–61. http://dx.doi.org/10.1021/nl201944h.

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Solov'ev, N. E., V. S. Makarov, L. N. Meshchaninova et Ya A. Ugai. « Interaction of oxides of 3d transition metals with boron ». Journal of Alloys and Compounds 178, n^o 1-2 (février 1992) : 131–38. http://dx.doi.org/10.1016/0925-8388(92)90254-7.

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Oishi, Masatsugu, Keiji Shimoda, Sojiro Okada, Ryoshi Imura, Keisuke Yamanaka, Hisao Yamashige, Hitoshi Mizuguchi, Iwao Watanabe, Yoshiharu Uchimoto et Toshiaki Ohta. « Evaluation of oxygen contribution on delithiation process of Li-rich layered 3d transition metal oxides ». Materials Today Communications 25 (décembre 2020) : 101673. http://dx.doi.org/10.1016/j.mtcomm.2020.101673.

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Pei, Yi, Qing Chen, Meiyu Wang, Bin Li, Peng Wang, Graeme Henkelman, Liang Zhen, Guozhong Cao et Cheng-Yan Xu. « Reviving reversible anion redox in 3d-transition-metal Li rich oxides by introducing surface defects ». Nano Energy 71 (mai 2020) : 104644. http://dx.doi.org/10.1016/j.nanoen.2020.104644.

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Wang, Kexin, Xinyue Wang, Zhongjian Li, Bin Yang, Min Ling, Xiang Gao, Jianguo Lu et al. « Designing 3d dual transition metal electrocatalysts for oxygen evolution reaction in alkaline electrolyte : Beyond oxides ». Nano Energy 77 (novembre 2020) : 105162. http://dx.doi.org/10.1016/j.nanoen.2020.105162.

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Frantzeskakis, Emmanouil, Tobias Chris Rödel, Franck Fortuna et Andrés Felipe Santander-Syro. « 2D surprises at the surface of 3D materials : Confined electron systems in transition metal oxides ». Journal of Electron Spectroscopy and Related Phenomena 219 (août 2017) : 16–28. http://dx.doi.org/10.1016/j.elspec.2016.10.001.

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