Petersen Thorben, Prodan Lilian, Tsurkan Vladimir, Krug von Nidda Hans-Albrecht, Kézsmárki István, Rößler Ulrich K, Hozoi Liviu
Institute for Theoretical Solid State Physics, Leibniz IFW Dresden, Helmholtzstraße 20, D-01069 Dresden, Germany.
Experimental Physics V, Center for Electronic Correlations and Magnetism, Institute of Physics, University of Augsburg, D-86159 Augsburg, Germany.
J Phys Chem Lett. 2022 Feb 24;13(7):1681-1686. doi: 10.1021/acs.jpclett.1c04100. Epub 2022 Feb 11.
Spin-orbit quartet ground states are associated with rich phenomenology, ranging from multipolar phases in f rare-earth borides to magnetism emerging through covalency and vibronic couplings in d transition-metal compounds. The latter effect has been studied since the 1960s on t octahedral units in both molecular complexes and extended solid-state lattices. Here we analyze the = 3/2 quartet ground state of larger cubane-like entities in lacunar spinels, composed of transition-metal () tetrahedra caged by chalcogenide ligands (). These represent a unique platform where spin-orbit coupling acts on molecular-like, delocalized t orbitals. Using quantum chemical methods, we pin down the interplay of spin-orbit couplings in such a setting and many-body physics related to other molecular-like single-electron levels, both below and above the reference t. We provide a different interpretation of resonant inelastic X-ray scattering data on GaTaSe and, by comparing magnetic susceptibility data with calculated factors, valuable insights into the important role of vibronic couplings.
自旋 - 轨道四重态基态与丰富的现象学相关联，范围从f稀土硼化物中的多极相到d过渡金属化合物中通过共价性和电子 - 振动耦合出现的磁性。自20世纪60年代以来，后一种效应已在分子配合物和扩展固态晶格中的八面体单元上进行了研究。在这里，我们分析了缺隙尖晶石中由硫族化物配体（）笼蔽的过渡金属（）四面体组成的类似立方烷的较大实体的J = 3/2四重态基态。这些代表了一个独特的平台，其中自旋 - 轨道耦合作用于类似分子的离域t轨道。使用量子化学方法，我们确定了在这种情况下自旋 - 轨道耦合的相互作用以及与参考t能级之下和之上的其他类似分子的单电子能级相关的多体物理学。我们对GaTaSe上的共振非弹性X射线散射数据提供了不同的解释，并通过将磁化率数据与计算的g因子进行比较，对电子 - 振动耦合的重要作用有了宝贵的见解。
