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• W2037707464 endingPage "1451" @default.
• W2037707464 startingPage "1442" @default.
• W2037707464 abstract "It is pointed out that interactions between octahedral-site cations are cation-anion-cation interactions if the cation-occupied octahedra share a common corner, but may be primarily cation- -cation (no anion intermediary) if the cation-occupied octahedra share either a common edge or a common face. It is further pointed out that cation- -cation interactions may be naturally classified as strong or weak since there is a critical cation separation below which the interacting electrons are best described by a collective-electron model, above which by a Heitler-London model. The characteristics of the different interactions under varying conditions are summarized. In the case of strong cation- -cation interactions, covalent-type bonds may be formed at low temperatures. The resulting phase transitions are marked by the following features: (1) the transitions may be noncooperative (isolated cation-cation pairing introducing no symmetry change to the structure) and extend over a considerable temperature interval ($ensuremath{Delta}Tensuremath{sim}100ifmmode^circelsetextdegreefi{}$C), or cooperative, occurring at a definite temperature and exhibiting thermal hysteresis. (2) Bonded cations are displaced from the center of symmetry of their anion interstice (in contrast to Jahn-Teller or spin-orbit distortions). (3) Bonding electrons are spin-paired so that they make no contribution to the atomic moment unless localized, unpaired $d$ electrons are simultaneously present to weaken the covalent-type bond via intra-atomic exchange. (4) Bonding electrons cannot contribute to metallic-type conductivity so that if the bond-forming phase ties up all of the outer $d$ electrons in covalent-type bonds, the transition is semiconducting ensuremath{rightleftharpoons} metallic. The physical properties of several compounds that illustrate the importance of the cation- -cation interactions are discussed." @default.
• W2037707464 created "2016-06-24" @default.
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• W2037707464 date "1960-03-15" @default.
• W2037707464 modified "2023-10-12" @default.
• W2037707464 title "Direct Cation- -Cation Interactions in Several Oxides" @default.
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• W2037707464 doi "https://doi.org/10.1103/physrev.117.1442" @default.
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