论文标题

使用本地缩放和Perdew-Zunger自我相互作用方法研究屏障高度中的自我交流 - 错误

Study of self-interaction-errors in barrier heights using locally scaled and Perdew-Zunger self-interaction methods

论文作者

Mishra, Prakash, Yamamoto, Yoh, Johnson, J. Karl, Jackson, Koblar A., Zope, Rajendra R., Baruah, Tunna

论文摘要

我们研究了自我交织误差对化学反应屏障高度的影响。为此,我们使用著名的Perdew-Zunger [J. P. Perdew和A. Zunger,物理。 Rev. b,{\ bf 23},5048(1981)]自我相互作用 - 校正(PZSIC),以及最近开发的局部规模自我交互校正(LSIC)的两个变体[R. R. Zope \ textit {et al。},J。Chem。物理。 {\ bf 151},214108(2019)]研究BH76基准数据集的屏障高度。我们的结果表明,相对于局部密度近似(LDA),PZSIC,尤其是LSIC方法都改善了屏障高度。使用ISO-orbital指示器$ z $作为缩放系数的LSIC版本比使用轨道密度与总电子密度的比率使用轨道依赖性因子$ W $的替代版本具有更一致的改进。我们表明,使用自洽和无自相互作用的PZSIC密度评估的LDA能量可用于评估密度驱动的误差。发现BH76集的LDA反应屏障误差包含集合中包含的所有类型反应的密度驱动的明显驱动误差,但是由于在功能上添加SIC而引起的校正比源于氢转移反应的密度和非氢溶剂转移反应大小的密度大得多。

We study the effect of self-interaction errors on the barrier heights of chemical reactions. For this purpose we use the well-known Perdew-Zunger [J. P. Perdew and A. Zunger, Phys. Rev. B, {\bf 23}, 5048 (1981)] self-interaction-correction (PZSIC), as well as two variations of the recently developed, locally scaled self-interaction correction (LSIC) [R. R. Zope \textit{et al.}, J. Chem. Phys. {\bf 151}, 214108 (2019)] to study the barrier heights of the BH76 benchmark dataset. Our results show that both PZSIC and especially the LSIC methods improve the barrier heights relative to the local density approximation (LDA). The version of LSIC that uses the iso-orbital indicator $z$ as a scaling factor gives a more consistent improvement than an alternative version that uses an orbital-dependent factor $w$ based on the ratio of orbital densities to the total electron density. We show that LDA energies evaluated using the self-consistent and self-interaction-free PZSIC densities can be used to assess density-driven errors. The LDA reaction barrier errors for the BH76 set are found to contain significant density-driven errors for all types of reactions contained in the set, but the corrections due to adding SIC to the functional are much larger than those stemming from the density for the hydrogen transfer reactions and of roughly equal size for the non-hydrogen transfer reactions.

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