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Static Polarizabilities at the Basis Set Limit: A Benchmark of 124 Species.
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2020-06-16 , DOI: 10.1021/acs.jctc.0c00128
Anders Brakestad 1 , Stig Rune Jensen 1 , Peter Wind 1 , Marco D'Alessandro 2 , Luigi Genovese 3 , Kathrin Helen Hopmann 1 , Luca Frediani 1
Affiliation  

Benchmarking molecular properties with Gaussian-type orbital (GTO) basis sets can be challenging, because one has to assume that the computed property is at the complete basis set (CBS) limit, without a robust measure of the error. Multiwavelet (MW) bases can be systematically improved with a controllable error, which eliminates the need for such assumptions. In this work, we have used MWs within Kohn–Sham density functional theory to compute static polarizabilities for a set of 92 closed-shell and 32 open-shell species. The results are compared to recent benchmark calculations employing the GTO-type aug-pc4 basis set. We observe discrepancies between GTO and MW results for several species, with open-shell systems showing the largest deviations. Based on linear response calculations, we show that these discrepancies originate from artifacts caused by the field strength and that several polarizabilies from a previous study were contaminated by higher order responses (hyperpolarizabilities). Based on our MW benchmark results, we can affirm that aug-pc4 is able to provide results close to the CBS limit, as long as finite difference effects can be controlled. However, we suggest that a better approach is to use MWs, which are able to yield precise finite difference polarizabilities even with small field strengths.

中文翻译:

静态极化率达到设定的上限:124个物种的基准。

使用高斯型轨道(GTO)基集对分子特性进行基准测试可能具有挑战性,因为人们必须假定计算出的特性处于完整基集(CBS)的极限,而没有可靠的误差度量。多小波(MW)基可以通过可控制的误差得到系统地改进,从而消除了此类假设的需要。在这项工作中,我们使用了Kohn-Sham密度泛函理论中的MWs来计算92个闭壳物种和32个开壳物种的静态极化率。将结果与采用GTO型aug-pc4基集的最新基准计算进行比较。我们观察到几种物种的GTO和MW结果之间存在差异,其中开壳系统显示出最大的偏差。根据线性响应计算,我们表明,这些差异是由磁场强度引起的伪影引起的,并且先前研究中的几个极化率都受到较高阶响应(超极化率)的污染。根据我们的MW基准测试结果,我们可以肯定aug-pc4能够提供接近CBS极限的结果,只要可以控制有限的差异效应即可。但是,我们建议一种更好的方法是使用MW,即使在较小的场强下也能产生精确的有限差分极化率。
更新日期:2020-08-11
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