Why is the Energy of the Singly Occupied Orbital in Some Radicals below the Highest Occupied Orbital Energy?
Why is the Energy of the Singly Occupied Orbital in Some Radicals below the Highest Occupied Orbital Energy?
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DOI：
10.1021/acs.chemmater.1c00683
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发表时间：
2021-05-13
影响因子：
8.6
通讯作者：
Autschbach, Jochen
中科院分区：
文献类型：
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作者：
Abella, Laura;Crassous, Jeanne;Autschbach, Jochen
单占据分子轨道（SOMO）能量低于最高占据分子轨道（HOMO）能级的有机（单）自由基近年来引起了人们的广泛关注。清楚地了解导致这种高能SOMO/HOMO反转（SHI）的电子因素将有助于合理设计具有高稳定性和其他期望性能的SHI自由基。计算研究了已知SHI自由基中影响SHI的电子因素。然后，将这些发现应用于“在硅”中设计潜在的SHI候选物。前沿轨道间的静电斥力以及封闭壳层“母体”化合物中轨道自旋分量和自旋分量之间的斥力是理解自由基中SHI发生的关键。
Organic (mono)radicals where the singly occupied molecular orbital (SOMO) is energetically below the highest occupied molecular orbital (HOMO) level have recently attracted much interest. A clear understanding of the electronic factors that lead to this energetic SOMO/HOMO inversion (SHI) would be desirable to aid the rational design of SHI radicals with high stability and other desired properties. The electronic factors that govern SHI in known SHI radicals are studied computationally. Then, the findings are applied to design potential SHI candidates 'in silico'. The electrostatic repulsion among the frontier orbitals and the repulsion between the alpha and beta spin components of the orbitals in a closed-shell 'parent' compound are key to understanding the occurrence of SHI in a radical.