Structural diradical character,Journal of Computational Chemistry

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Structural diradical character
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2018-12-27 , DOI: 10.1002/jcc.25768
Bodo Alexander Voigt ₁ , Torben Steenbock ₂ , Carmen Herrmann ₁

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A reliable first‐principles description of singlet diradical character is essential for predicting nonlinear optical and magnetic properties of molecules. As diradical and closed‐shell electronic structures differ in their distribution of single, double, triple, and aromatic bonds, modeling electronic diradical character requires accurate bond‐length patterns, in addition to accurate absolute bond lengths. We therefore introduce structural diradical character, which we suggest as an additional measure for comparing first‐principles calculations with experimental data. We employ this measure to identify suitable exchange–correlation functionals for predicting the bond length patterns and electronic diradical character of a biscobaltocene with the potential for photoswitchable nonlinear optical activity. Out of four popular approximate exchange–correlation functionals with different exact‐exchange admixtures (BP86, TPSS, B3LYP, TPSSh), the two hybrid functionals TPSSh and B3LYP perform best for diradical bond length patterns, with TPSSh being best for the organometallic validation systems and B3LYP for the organic ones (for which the D3 dispersion correction was included). Still, none of the functionals is suitable for correctly describing relative bond lengths across the range of molecules studied, so that none can be recommended for predictive studies of (potential) diradicals without reservation. © 2018 Wiley Periodicals, Inc.

中文翻译：

结构双基字符

单线态双自由基特征的可靠第一性原理描述对于预测分子的非线性光学和磁性特性至关重要。由于双自由基和闭壳电子结构在单键、双键、三键和芳香键的分布上有所不同，因此除了准确的绝对键长之外，对电子双自由基特征建模还需要准确的键长模式。因此，我们引入了结构双自由基特征，我们建议将其作为将第一性原理计算与实验数据进行比较的附加措施。我们采用这种措施来确定合适的交换相关函数，以预测具有光可开关非线性光学活性潜力的双钴茂的键长模式和电子双自由基特征。在具有不同精确交换混合物（BP86、TPSS、B3LYP、TPSSh）的四种流行的近似交换相关泛函中，两种混合泛函 TPSSh 和 B3LYP 对双自由基键长模式表现最佳，TPSSh 最适用于有机金属验证系统和B3LYP 用于有机物（包括 D3 色散校正）。尽管如此，没有一个泛函适合正确描述所研究分子范围内的相对键长，因此不能毫无保留地推荐用于（潜在）双自由基的预测研究。© 2018 Wiley Periodicals, Inc. TPSSh 最适合有机金属验证系统，B3LYP 最适合有机验证系统（其中包括 D3 色散校正）。尽管如此，没有一个泛函适合正确描述所研究分子范围内的相对键长，因此不能毫无保留地推荐用于（潜在）双自由基的预测研究。© 2018 Wiley Periodicals, Inc. TPSSh 最适合有机金属验证系统，B3LYP 最适合有机验证系统（其中包括 D3 色散校正）。尽管如此，没有一个泛函适合正确描述所研究分子范围内的相对键长，因此不能毫无保留地推荐用于（潜在）双自由基的预测研究。© 2018 Wiley Periodicals, Inc.

更新日期：2018-12-27

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