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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Tolerance Factor and Cation-Anion Orbital Interactions Differentiating the Polar and Antiferrodistortive Structures of Perovskite Oxides ABO(3)
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Tolerance Factor and Cation-Anion Orbital Interactions Differentiating the Polar and Antiferrodistortive Structures of Perovskite Oxides ABO(3)

机译:钙钛矿型氧化物ABO(3)的极性和反铁畸变结构的宽容因子和阳离子-阴离子轨道相互作用

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摘要

We explored under what conditions perovskite oxides ABO(3) adopt a polar or an antiferrodistortive structure from the viewpoint of the tolerance factor tau and the orbital interactions of the empty orbitals of the A and B cations with the filled orbitals of their surrounding O2- ions. Polar structures require the presence of a substantial size-mismatch as well as strong cation-anion orbital interactions at A or B cation sites. A tetragonal polar structure is preferred when the A cation empty orbitals are extended or when the B-cation empty orbitals are contracted. A trigonal polar structure is favored in opposite cases. An antiferrodistortive structure is found for perovskites with weak size-mismatch or those with substantial size-mismatch if both A and B cations do not generate strong cation-anion orbital interactions. Antiferrodistortive structures result from interactions involving the A cations with the O-4 squares of the face-sharing AO(8) square-prisms in a two-in-two-out manner, and are found only when the A/O cation-anion interactions are substantial.
机译:我们从容忍因子tau以及A和B阳离子的空轨道与其周围的O2-离子的填充轨道的相互作用的角度探讨了钙钛矿氧化物ABO(3)在什么条件下采用极性或反铁畸变结构。极性结构要求在A或B阳离子位点存在明显的尺寸不匹配以及强烈的阳离子-阴离子轨道相互作用。当A阳离子的空轨道伸展时或当B阳离子的空轨道收缩时,四方极性结构是优选的。在相反的情况下,三角形极结构是有利的。如果A和B阳离子均不产生强阳离子-阴离子轨道相互作用,则发现钙钛矿的反铁变形结构具有弱的尺寸失配或钙钛矿的尺寸失配。反铁畸变结构是由A阳离子与面部共享AO(8)方形棱镜的O-4正方形以二进二出的方式相互作用而产生的,并且仅在A / O阳离子为阴离子时才能发现互动是实质性的。

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