The Mechanism of Spin-Phonon Relaxation in Endohedral Metallofullerene Single Molecule Magnets

IF 7.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science Pub Date : 2025-06-09 DOI:10.1039/d4sc07786e

Tanu Sharma, Rupesh Kumar Tiwari, Sourav Dey, Antonio Mariano, Alessandro Lunghi, Gopalan Rajaraman

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引用次数: 0

Abstract

This study presents the first-ever investigation of spin-phonon coupling mechanisms in fullerene-based single-molecule magnets (SMMs) using ab initio CASSCF combined with DFT calculations. While lanthanide-based SMMs, particularly those with DyIII ions, are known for their impressive blocking temperatures and relaxation barriers, endohedral metallofullerene (EMFs) offer a unique platform for housing low-coordinated lanthanides within rigid carbon cages. We have explored the spin dynamics of in DyScS@C82 exhibiting among the highest blocking temperature (TB) reported. Through our computational analysis, we reveal that while the fullerene cage enhances crystal field splitting and provides structural stability without significantly contributing to spin-relaxation-driving low-energy phonons, the internal ionic motion emerges as the primary factor controlling spin relaxation and limiting blocking temperature. This computational investigation into the spin dynamics of EMF-based SMMs provides key insights into their magnetic behaviour for the first time and suggests potential strategies for improving their performance towards futuristic SMMs.

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内嵌金属富勒烯单分子磁体的自旋声子弛豫机制

本研究首次使用从头算CASSCF结合DFT计算对富勒烯基单分子磁体（SMMs）中的自旋声子耦合机制进行了研究。虽然基于镧系元素的smm，特别是那些具有DyIII离子的smm，以其令人印象深刻的阻断温度和弛豫屏障而闻名，但内质金属富勒烯（emf）为在刚性碳笼中容纳低配位镧系元素提供了独特的平台。我们已经探索了in DyScS@C82的自旋动力学，显示出最高的阻断温度（TB）。通过我们的计算分析，我们发现虽然富勒烯笼增强了晶体场分裂并提供了结构稳定性，但没有显著贡献自旋弛豫驱动的低能声子，内部离子运动成为控制自旋弛豫和限制阻挡温度的主要因素。这项对基于emf的smm自旋动力学的计算研究首次提供了对其磁性行为的关键见解，并提出了改善其未来smm性能的潜在策略。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Chemical Science CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

4.80%

发文量

1352

审稿时长

2.1 months

期刊介绍： Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.