Reliable prediction of association (free) energies of supramolecular complexes with heavy main group elements – the HS13L benchmark set,Physical Chemistry Chemical Physics

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Reliable prediction of association (free) energies of supramolecular complexes with heavy main group elements – the HS13L benchmark set
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2022-11-24 , DOI: 10.1039/d2cp04049b
Johannes Gorges ₁ , Stefan Grimme ₁ , Andreas Hansen ₁

Affiliation

We introduce a set of 13 supramolecular complexes featuring diverse non-covalent interactions with heavy main group elements (Zn, As, Se, Te, Br, I), high charges (−2 up to +4), and large systems with up to 266 atoms (HS13L). The experimental Gibbs free energies of association cover the typical range (−1.9 to −9.2 kcal mol⁻¹). An efficient automated multilevel theoretical workflow is applied for the determination of the respective minimum structures in solution by conformer ensemble generation with the CREST program at the semiempirical GFN2-xTB level. Subsequent refinement is performed with the r²SCAN-3c composite DFT method including thermostatistical corrections at the GFN2-xTB level and solvation contributions by COSMO-RS using the CENSO free energy ranking algorithm. Various density functional approximations in combination with three London dispersion correction schemes are assessed against “back-corrected” experimental association energies as well as accurate local coupled cluster reference values. Our protocol predicts association free energies with a mean absolute deviation of only 2 kcal mol⁻¹ from the measured values. Thus, it is well suited to generate reference association free energies for assessing theoretical methods on realistically sized supramolecular complexes or to support experimental chemists. For specifically evaluating methods for calculating gas-phase association energies, we recommend using the provided accurate coupled cluster reference values. We propose to use this set as an extension of the S30L benchmark set [Sure et al., J. Chem. Theory Comput., 2015, 11, 3785–3801] with a special focus on the challenging computation of non-covalent interactions of heavy main group elements.

中文翻译：

具有重主族元素的超分子配合物的缔合（自由）能的可靠预测——HS13L 基准组

我们介绍了一组 13 种超分子复合物，它们具有与重主族元素（Zn、As、Se、Te、Br、I）、高电荷（-2 至 +4）和高达266 个原子（HS13L）。实验吉布斯缔合自由能涵盖典型范围（-1.9 至-9.2 kcal mol ^-1）。在半经验 GFN2-xTB 水平上，通过使用CREST程序的构象合奏生成，应用高效的自动化多级理论工作流程来确定解决方案中的相应最小结构。随后使用 r ² SCAN-3c 复合 DFT 方法进行改进，包括 GFN2-xTB 水平的热统计校正和 COSMO-RS 使用 CENSO 的溶剂化贡献自由能排序算法。各种密度泛函近似与三种伦敦色散校正方案相结合，根据“反向校正”实验关联能量以及准确的局部耦合簇参考值进行评估。我们的方案预测结合自由能与测量值的平均绝对偏差仅为 2 kcal mol ^{-1 。}因此，它非常适合生成参考缔合自由能，用于评估实际大小的超分子复合物的理论方法或支持实验化学家。对于计算气相缔合能的具体评估方法，我们建议使用提供的精确耦合簇参考值。我们建议使用此集作为 S30L 基准集的扩展 [确定等。, J. 化学。理论计算。, 2015, 11 , 3785–3801] 特别关注重主族元素非共价相互作用的挑战性计算。

更新日期：2022-11-24

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