Spin density accuracy and distribution in azido Cu(II) complexes: A source function analysis,Journal of Computational Chemistry

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Spin density accuracy and distribution in azido Cu(II) complexes: A source function analysis
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2018-01-05 , DOI: 10.1002/jcc.25150
Giovanni Macetti ₁ , Leonardo Lo Presti ₁ , Carlo Gatti ₂

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Magnetic properties of open‐shell systems depend on their unpaired electron density distribution. Accurate spin density (SD) is difficult to retrieve, both from polarized neutron diffraction (PND) data and from quantum approaches, and its interpretation is not trivial. The Source Function is a useful tool to interpret SD distributions and their accuracy. It is here applied to analyze and compare the theoretical SD in a weakly ferromagnetically coupled end‐end azido dicopper complex with that in a strongly‐coupled end‐on complex. The Source Function enables to highlight the origin of the SD differences between the two dicopper complexes and among adopted computational approaches (CASSCF, DFT, UHF). Further insight is provided by partial Source Function SD reconstructions using given subsets of atoms. DFT methods exaggerate electron sharing between copper and the ligands, causing spin delocalization toward them and overestimating metal‐ligand spin polarization, while underestimating CASSCF spin information transmission between atoms. CAS(10,10) SD is closer to the PND SD than other adopted methods © 2018 Wiley Periodicals, Inc.

中文翻译：

叠氮铜 (II) 配合物中的自旋密度精度和分布：源函数分析

开壳系统的磁性取决于它们的不成对电子密度分布。很难从极化中子衍射 (PND) 数据和量子方法中检索准确的自旋密度 (SD)，其解释也很重要。源函数是解释 SD 分布及其准确性的有用工具。此处应用于分析和比较弱铁磁耦合端-端叠氮二铜配合物与强耦合端-端复合物的理论 SD。源函数能够突出两种双铜配合物之间以及采用的计算方法（CASSCF、DFT、UHF）之间 SD 差异的起源。使用给定原子子集的部分源函数 SD 重建提供了进一步的见解。DFT 方法夸大了铜和配体之间的电子共享，导致它们的自旋离域并高估了金属配体的自旋极化，同时低估了原子之间的 CASSCF 自旋信息传输。CAS(10,10) SD 比其他采用的方法更接近 PND SD © 2018 Wiley Periodicals, Inc.

更新日期：2018-01-05

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