Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Ministry of Education Key Laboratory of Computational Physical Sciences, Department of Chemistry, Fudan University, Shanghai 200433, China.
Hefei National Laboratory, Hefei 230088, China.
J Chem Theory Comput. 2023 Jun 13;19(11):3112-3122. doi: 10.1021/acs.jctc.3c00025. Epub 2023 May 9.
Static polarizability is an important ingredient for describing optical phenomena, intermolecular interactions, etc. It also offers a way to gauge the accuracy of the electronic structure methods. However, polarizability data sets that include a large variety of species with high-quality reference data are still lacking. In this work, we calibrate the reference data of two existing data sets, HR46 (Hickey and Rowley 2014, 118, 3678-3687.) and T145 (Thakkar et al. 2015, 635, 257-261.), consisting of molecules with sizes up to 15 atoms. We apply the focal-point analysis (FPA) to the isotropic and anisotropic polarizability calculations, achieving the MP2 correlation contribution by the complete basis set (CBS) extrapolation of aug-cc-pCV[Q5]Z, augmented by the CCSD(T) correlation contribution from the CBS extrapolation of aug-cc-pV[XY]Z with [XY] = [Q5], [TQ], and [DT], respectively, to accommodate the computation to the system size. We conclude that our reference data are close to the CCSD(T)/aug-cc-pCV[Q5]Z quality, which are beneficial to the future assessment and benchmark studies of other electronic structure methods, in particular, density functional approximations.
静态极化率是描述光学现象、分子间相互作用等的重要因素。它还提供了一种衡量电子结构方法准确性的方法。然而，仍然缺乏包含具有高质量参考数据的多种物种的极化率数据集。在这项工作中，我们校准了两个现有数据集 HR46（Hickey 和 Rowley 2014，118，3678-3687.）和 T145（Thakkar 等人，2015，635，257-261.）的参考数据，这些数据集由大小高达 15 个原子的分子组成。我们将焦点分析（FPA）应用于各向同性和各向异性极化率计算，通过 aug-cc-pCV[Q5]Z 的完全基组（CBS）外推实现 MP2 相关贡献，并通过 aug-cc-pV[XY]Z 的 CBS 外推从 CCSD(T)相关贡献进行补充，其中 [XY] = [Q5]、[TQ] 和 [DT]，分别适应系统大小的计算。我们得出结论，我们的参考数据接近 CCSD(T)/aug-cc-pCV[Q5]Z 的质量，这有利于未来对其他电子结构方法的评估和基准研究，特别是密度泛函近似。
