论文标题
电子和磁能尺度的化学设计
Chemical Design of Electronic and Magnetic Energy Scales in Tetravalent Praseodymium
论文作者
论文摘要
通常使用导致局部磁矩的离子图片来描述三价氧化态的灯笼。与三价灯笼相关的分层能量尺度产生理想的特性，例如分子磁，量子材料和量子转导。在这里，我们表明，这种传统的离子范式在4+氧化状态下为praseodymium崩溃。部署在几种固态PR4+氧化物上的合成，光谱和理论工具发现了4F轨道在粘结中的异常参与以及与过渡金属类似的配体价电子的4F1构型与配体价电子的异常杂交。晶体场和自旋轨道偶联相互作用之间的竞争从根本上转化了PR4+的自旋轨道磁性，后者偏离了Jeff = 1/2的限制，并且类似于高价值acTacinides。我们的结果表明，PR4+离子本身就是一个类别，可以量身定制单离子能量尺度的层次结构，以探索量子材料中的新相关现象。
Lanthanides in the trivalent oxidation state are typically described using an ionic picture that leads to localized magnetic moments. The hierarchical energy scales associated with trivalent lanthanides produce desirable properties for e.g., molecular magnetism, quantum materials, and quantum transduction. Here, we show that this traditional ionic paradigm breaks down for praseodymium in the 4+ oxidation state. Synthetic, spectroscopic, and theoretical tools deployed on several solid-state Pr4+ oxides uncover the unusual participation of 4f orbitals in bonding and the anomalous hybridization of the 4f1 configuration with ligand valence electrons, analogous to transition metals. The resulting competition between crystal-field and spin-orbit-coupling interactions fundamentally transforms the spin-orbital magnetism of Pr4+, which departs from the Jeff =1/2 limit and resembles that of high-valent actinides. Our results show that Pr4+ ions are in a class on their own, where the hierarchy of single-ion energy scales can be tailored to explore new correlated phenomena in quantum materials.
