A Complete Ab Initio View of Orbach and Raman Spin-Lattice Relaxation in a Dysprosium Coordination Compound.
A Complete Ab Initio View of Orbach and Raman Spin-Lattice Relaxation in a Dysprosium Coordination Compound.
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在不良配位化合物中，Orbach和Raman Spin-lattice松弛的完整视图。
DOI：
10.1021/jacs.1c05068
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发表时间：
2021-09-01
影响因子：
15
通讯作者：
Lunghi A
中科院分区：
文献类型：
--
作者：
Briganti M;Santanni F;Tesi L;Totti F;Sessoli R;Lunghi A
镧系元素分子复合物独特的电子和磁性使其处于高温单分子磁体和磁性量子比特竞赛的最前沿。迄今为止，这类化合物的设计几乎完全由静态晶场考虑驱动，重点是增加磁各向异性势垒。现在，这一指导方针已经达到了最大的潜力，更深入地了解自旋-声子弛豫机制是推动合成化学超越简单直觉的关键。在这项工作中，我们计算弛豫时间完全从头算和揭示的性质，所有自旋-声子弛豫机制，即Orbach和拉曼途径，在一个典型的Dy单分子磁体。计算预测与自旋弛豫时间和晶场各向异性的实验测定相一致，并表明拉曼弛豫，在低温下占主导地位，是由低能声子引发的，并没有受到进一步的工程晶场轴性的影响。对自旋-声子耦合机制的综合分析表明，离子第一配位壳层以外的分子振动也可以通过静电极化效应在自旋弛豫中发挥重要作用。因此，这项工作通过提供一套新颖而完整的化学设计规则来解决任何温度下自旋弛豫的各个方面，为该领域的发展指明了方向。
The unique electronic and magnetic properties of lanthanide molecular complexes place them at the forefront of the race toward high-temperature single-molecule magnets and magnetic quantum bits. The design of compounds of this class has so far being almost exclusively driven by static crystal field considerations, with an emphasis on increasing the magnetic anisotropy barrier. Now that this guideline has reached its maximum potential, a deeper understanding of spin-phonon relaxation mechanisms presents itself as key in order to drive synthetic chemistry beyond simple intuition. In this work, we compute relaxation times fully ab initio and unveil the nature of all spin-phonon relaxation mechanisms, namely Orbach and Raman pathways, in a prototypical Dy single-molecule magnet. Computational predictions are in agreement with the experimental determination of spin relaxation time and crystal field anisotropy, and show that Raman relaxation, dominating at low temperature, is triggered by low-energy phonons and little affected by further engineering of crystal field axiality. A comprehensive analysis of spin-phonon coupling mechanism reveals that molecular vibrations beyond the ion’s first coordination shell can also assume a prominent role in spin relaxation through an electrostatic polarization effect. Therefore, this work shows the way forward in the field by delivering a novel and complete set of chemically sound design rules tackling every aspect of spin relaxation at any temperature.
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影响因子：
8.4
作者：
Escalera-Moreno, Luis;Baldovi, Jose J.;Coronado, Eugenio
通讯作者：
Coronado, Eugenio
影响因子：
21.8
作者：
Gaita-Arino, A.;Luis, F.;Coronado, E.
通讯作者：
Coronado, E.
影响因子：
4.6
作者：
Escalera-Moreno, Luis;Baldovi, Jose J.;Coronado, Eugenio
通讯作者：
Coronado, Eugenio
影响因子：
15
作者：
Briganti M;Lucaccini E;Chelazzi L;Ciattini S;Sorace L;Sessoli R;Totti F;Perfetti M
通讯作者：
Perfetti M
影响因子：
4.6
作者：
Albino, Andrea;Benci, Stefano;Lunghi, Alessandro
通讯作者：
Lunghi, Alessandro