论文标题

基于分子核心级$ GW $计算的选择

On the basis set selection for molecular core-level $GW$ calculations

论文作者

Mejia-Rodriguez, Daniel, Kunitsa, Alexander, Aprà, Edoardo, Govind, Niranjan

论文摘要

$ GW $近似最近在模拟分子核心X射线光发射光谱的方法中越来越受欢迎。传统上,$ GW $核心级别的绑定能量是使用CC-PV $ n $ Z或DEF2- $ n $ ZVP基套基集的家族计算的,将所获得的结果推到完整的基集限制,然后进行元素特定的相关性校正。尽管具有良好的精度,但这些结合能仍被长期低估。通过使用已知在其他理论中提供良好成本准确比率的第一行元素和标准技术,我们表明CC-PV $ n $ z和def2- $ n $ ZVP系列显示出较大的收缩错误,并导致不可靠的完整基础设置集合。另一方面,我们证明了这些基础集的未合同版本提供了大大改善的融合。甚至可以使用核心丰富的,属性优化的基础设置的核心融合,例如PCSSEG- $ N $,PCJ-$ N $和CCX- $ N $ Z。最后,我们还表明,对核心属性的改进不会降低价值的计算,从而提供了对核心区域和价值区域的平衡描述。

The $GW$ approximation has been recently gaining popularity among the method for simulating molecular core-level X-ray photoemission spectra. Traditionally, $GW$ core-level binding energies have been computed using either the cc-pV$n$Z or def2-$n$ZVP basis set families, extrapolating the obtained results to the complete basis set limit, followed by a an element-specific relativistic correction. Despite of achieving good accuracy, these binding energies are chronically underestimated. By using first-row elements and standard techniques known to offer good cost-accuracy ratio in other theories, we show that the cc-pV$n$Z and def2-$n$ZVP families show large contraction errors and lead to unreliable complete basis set extrapolations. On the other hand, we demonstrate that uncontracted versions of these basis sets offer vastly improved convergence. Even faster convergence can be obtained using core-rich, property-optimized, basis sets families like pcSseg-$n$, pcJ-$n$ and ccX-$n$Z. Finally, we also show that the improvement over the core properties does not degrade the calculation of the valence excitations, and thus offer a balanced description of both core and valence regions.

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