Escalera-Moreno Luis, Baldoví José J, Gaita-Ariño Alejandro, Coronado Eugenio
Instituto de Ciencia Molecular (ICMol) , Universitat de València , c/ Catedrático José Beltrán 2 , Paterna , 46980 , Spain . Email:
Chem Sci. 2019 Dec 2;11(6):1593-1598. doi: 10.1039/c9sc03133b. eCollection 2020 Feb 14.
One of the main roadblocks that still hamper the practical use of molecular nanomagnets is their cryogenic working temperature. In the pursuit of rational strategies to design new molecular nanomagnets with increasing blocking temperature, methodologies play an important role by guiding synthetic efforts at the lab stage. Nevertheless, when evaluating vibration-induced spin relaxation, these methodologies are still far from being computationally fast enough to provide a useful predictive framework. Herein, we present an inexpensive first-principles method devoted to evaluating vibration-induced spin relaxation in molecular -block single-ion magnets, with the important advantage of requiring only one CASSCF calculation. The method is illustrated using two case studies based on uranium as the magnetic centre. Finally, we propose chemical modifications in the ligand environment with the aim of suppressing spin relaxation.
仍然阻碍分子纳米磁体实际应用的主要障碍之一是它们的低温工作温度。在寻求设计具有不断提高的阻塞温度的新型分子纳米磁体的合理策略时，方法学在实验室阶段指导合成工作中发挥着重要作用。然而，在评估振动诱导的自旋弛豫时，这些方法在计算速度上仍远不足以提供一个有用的预测框架。在此，我们提出一种廉价的第一性原理方法，专门用于评估分子块单离子磁体中振动诱导的自旋弛豫，其重要优点是只需要一次完全活性空间自洽场（CASSCF）计算。该方法通过基于铀作为磁中心的两个案例研究进行了说明。最后，我们提出了在配体环境中进行化学修饰，以抑制自旋弛豫。
