Georgiev Miroslav, Chamati Hassan
Bulgarian Academy of Sciences, G Nadjakov Institute of Solid State Physics, Tsarigradsko Chaussée 72, 1784 Sofia, Bulgaria.
ACS Omega. 2023 Jul 21;8(31):28640-28650. doi: 10.1021/acsomega.3c03208. eCollection 2023 Aug 8.
This paper attempts to shed light on the origin of the magnetic behavior specific to trigonal bi- and pyramidal 3d mono- and polynuclear nanomagnets. The focus lies on entirely unraveling the system's intrinsic microscopic mechanisms and fundamental quantum mechanical relations governing the underlying electron dynamics. To this end, we develop a self-consistent approach to characterize, in great detail, all electron correlations and the ensuing fine structure of the energy spectra of a broad class of 3d systems. The mathematical framework is based on the multiconfigurational self-consistent field method and is devised to account for prospective quantum mechanical constraints that may confine the electron orbital dynamics while preserving the properties of all measurable quantities. We successfully characterize the experimentally observed magnetic anisotropy properties of a slightly distorted trigonal bipyramidal Ni coordination complex, demonstrating that such compounds do not exhibit intrinsic huge zero-field splitting and inherent giant magnetic anisotropy. We reproduce qualitatively and quantitatively the behavior of the low-field magnetic susceptibility, magnetization, low-, and high-field electron paramagnetic resonance spectroscopy measurements and provide an in-depth analysis of the obtained results.
本文试图阐明三角双锥和三角锥3d单核及多核纳米磁体特有的磁行为的起源。重点在于全面揭示系统内在的微观机制以及支配潜在电子动力学的基本量子力学关系。为此，我们开发了一种自洽方法，以详细表征广泛的3d系统中所有电子关联以及由此产生的能谱精细结构。该数学框架基于多组态自洽场方法，旨在考虑可能限制电子轨道动力学同时保留所有可测量量性质的潜在量子力学约束。我们成功地表征了轻微畸变的三角双锥Ni配位络合物的实验观测到的磁各向异性性质，表明此类化合物不表现出固有的巨大零场分裂和固有的巨磁各向异性。我们定性和定量地再现了低场磁化率、磁化强度、低场和高场电子顺磁共振光谱测量的行为，并对所得结果进行了深入分析。
