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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Computation of Dipole Moments: A Recommendation on the Choice of the Basis Set and the Level of Theory
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Computation of Dipole Moments: A Recommendation on the Choice of the Basis Set and the Level of Theory

机译：对偶极矩的计算：关于选择基础集的建议和理论水平

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摘要

Together with experimental data, theoretically predicted dipole moments represent a valuable tool for different branches in the chemical and physical sciences. With the diversity of levels of theory and basis sets available, a reliable combination must be carefully chosen in order to achieve accurate predictions. In a recent publication (J. Chem. Theory Comput. 2018, 14 (4), 1969-1981), Hait and Head-Gordon took a first step in this regard by providing recommendations on the best density functionals suitable for these purposes. However, no extensive study has been performed to provide recommendations on the basis set choice. Here, we shed some light into this matter by evaluating the performance of 38 general-purpose basis sets of single- up to triple-zeta-quality, when coupled with nine different levels of theory, in the computation of dipole moments. The calculations were performed on a data set with 114 small molecules containing second- and third-row elements. We based our analysis in regularized root-mean-square errors (regularized RMSE), in which the difference between the calculated mu(calc) and benchmark mu(bmk )dipole moment values is derived as (mu(calc)[D] - mu(bmk )[D])/(max(mu(bmk)[D],1[D])). This procedure ensures relative errors for ionic species and absolute errors for species with small dipole moment values. Our results indicate that the best compromise between accuracy and computational efficiency is achieved by performing the computations with an augmented double-C-quality basis set (i.e., aug-pc-1, aug-pcseg-1, aug-cc-pVDZ) together with a hybrid functional (e.g., omega B97X-V, SOGGA11-X). Augmented triple-zeta basis sets could enhance the accuracy of the computations, but the computational cost of introducing such a basis set is substantial compared with the small improvement provided. These findings also highlight the crucial role that augmentation of the basis set with diffuse functions on both hydrogen and non-hydrogen atoms plays in the computation of dipole moments.
机译：与实验数据一起，理论上预测的偶极矩代表了化学和物理学中不同分支的宝贵工具。随着理论和基础集水平的多样性，必须仔细选择可靠的组合，以实现准确的预测。在最近的出版物（J.Chem。理论计算。2018,14（4），1969-1981），HAIT和Head-Gordon在这方面迈出了关于适合这些目的的最佳密度函数的建议。但是，没有进行广泛的研究以提供关于基础设定选择的建议。在这里，我们通过评估偶极矩的计算时，通过评估38个通用基准组的表现，在偶极矩的计算中阐明了38个通用基础的性能。在具有114个小分子的数据集上进行计算，其中包含含有第二和第三行元素的114个小分子。我们基于我们在正则化的根均方误差（正则化RMSE）中的分析，其中计算的MU（CALC）和基​​准MU（BMK）偶极力矩值之间的差异是（MU（CALC）[D] - mu （BMK）[D]）/（MA（MU（BMK）[D]，1 [D]））。该过程确保离子物种的相对误差和具有小偶极力矩值的物种的绝对误差。我们的结果表明，通过使用增强双C基准组（即8AUG-PC-1，AUG-PCSEG-1，AUG-CC-PVDZ）在一起进行计算来实现精度和计算效率之间的最佳折衷具有混合功能（例如，OMEGA B97X-V，Sogga11-X）。增强三季度基础集可以提高计算的准确性，但引入这种基础集的计算成本与提供的小改进相比是大幅的。这些发现还突出了增强基础设定的重要作用，散氢和非氢原子在偶极矩的计算中起作用。

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