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Understanding the Structure and Ground State of the Prototype CuF2 Compound Not Due to the Jahn–Teller Effect
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2019-03-19 00:00:00 , DOI: 10.1021/acs.inorgchem.9b00178 José Antonio Aramburu 1 , Miguel Moreno 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2019-03-19 00:00:00 , DOI: 10.1021/acs.inorgchem.9b00178 José Antonio Aramburu 1 , Miguel Moreno 1
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Insulating CuF2 is considered a prototype compound displaying a Jahn–Teller effect (JTE) which gives rise to elongated CuF64– units. By means of first-principles calculations together with an analysis of experimental data of both CuF2 and Cu2+-doped ZnF2, we demonstrate that such an idea is not correct. For ZnF2:Cu2+, we find that CuF64– units are compressed always along the Z local axis with a hole essentially in a 3z2–r2 antibonding orbital, in agreement with experimental EPR data that already underline the absence of a JTE. The structure of the monoclinic CuF2 crystal also comes from compressed CuF64– complexes, although hidden by an additional orthorhombic instability due to a negative force constant of b2g and b3g local modes. The associated distortion, similar to that involved in K2CuF4 and other layered Cu2+ compounds, is also shown to be developed for ZnF2:Cu2+ upon increasing the copper concentration. The origin of this cooperative effect is discussed together with the differences between non-Jahn–Teller systems like ZnF2:Cu2+ and CuF2 and true Jahn–Teller systems like KZnF3:Cu2+. From present results and those on layered compounds, the usual assumption of a JTE for explaining the properties of d9 ions in low-symmetry lattices can hardly be right.
中文翻译：
理解不是由于Jahn-Teller效应引起的原型CuF 2化合物的结构和基态
绝缘CuF 2被认为是具有Jahn–Teller效应（JTE）的原型化合物，该化合物会产生细长的CuF 6 4–单元。通过第一性原理计算以及对CuF 2和Cu 2+掺杂的ZnF 2的实验数据的分析，我们证明了这种想法是不正确的。对于ZnF 2：Cu 2+，我们发现CuF 6 4–单元始终沿Z局部轴压缩，并在3 z 2 – r 2处有孔与已经证明缺乏JTE的实验性EPR数据相吻合的抗粘结轨道。单斜晶CuF 2晶体的结构也来自压缩的CuF 6 4–配合物，尽管由于b 2g和b 3g局部模态的负力常数而被附加的正交各向异性所掩盖。还显示出与ZnF 2：Cu 2+有关的与K 2 CuF 4和其他层状Cu 2+化合物所涉及的相似的畸变。在增加铜浓度时。讨论了这种协同效应的起源，以及非Jahn–Teller系统（如ZnF 2：Cu 2+和CuF 2）与真正的Jahn–Teller系统（如KZnF 3：Cu 2+）之间的差异。从目前的结果以及层状化合物的结果来看，JTE用来解释低对称晶格中d 9离子性质的通常假设几乎是不正确的。
更新日期：2019-03-19
中文翻译：
理解不是由于Jahn-Teller效应引起的原型CuF 2化合物的结构和基态
绝缘CuF 2被认为是具有Jahn–Teller效应（JTE）的原型化合物，该化合物会产生细长的CuF 6 4–单元。通过第一性原理计算以及对CuF 2和Cu 2+掺杂的ZnF 2的实验数据的分析，我们证明了这种想法是不正确的。对于ZnF 2：Cu 2+，我们发现CuF 6 4–单元始终沿Z局部轴压缩，并在3 z 2 – r 2处有孔与已经证明缺乏JTE的实验性EPR数据相吻合的抗粘结轨道。单斜晶CuF 2晶体的结构也来自压缩的CuF 6 4–配合物，尽管由于b 2g和b 3g局部模态的负力常数而被附加的正交各向异性所掩盖。还显示出与ZnF 2：Cu 2+有关的与K 2 CuF 4和其他层状Cu 2+化合物所涉及的相似的畸变。在增加铜浓度时。讨论了这种协同效应的起源，以及非Jahn–Teller系统（如ZnF 2：Cu 2+和CuF 2）与真正的Jahn–Teller系统（如KZnF 3：Cu 2+）之间的差异。从目前的结果以及层状化合物的结果来看，JTE用来解释低对称晶格中d 9离子性质的通常假设几乎是不正确的。
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