论文标题

了解反应屏障高度的密度驱动误差

Understanding density driven errors for reaction barrier heights

论文作者

Kaplan, Aaron D., Shahi, Chandra, Bhetwal, Pradeep, Sah, Raj K., Perdew, John P.

论文摘要

定位误差,例如电荷转移和一些自我交互错误,鼠疫计算效率和其他精确的密度功能近似(DFAS)。通常建议在Hartree-fock(HF)密度上评估半本地DFA,通常建议作为用于离域误差的计算廉价补救措施。对于像扫描等复杂的元数据,这种方法可以实现出色的准确性。当此HF-DFT(或DFA@HF)在DFA上显着改善时,通常认为HF密度比自洽的DFA密度更准确。通过应用密度校正密度功能理论(DFT)的指标,我们表明HF-DFT通过使本地化电荷传输误差或密度过度校正来适用于屏障高度,从而产生了对能量的密度和功能驱动驱动误差的某种可靠性。对少数过渡状态的电荷传输误差的定量分析证实了这一趋势。我们没有确切的功能和精确的密度来评估大型BH76屏障高度数据库的确切密度和功能驱动的误差。取而代之的是,我们已经识别并使用了三个非本地替代功能(扫描50%全球混合动力车,范围分离的混合LC-$ω$ PBE和SCAN-FLOSIC)及其自稳态密度。这些功能产生相当准确的自洽屏障高度,它们的自洽总能在分数电子数中几乎是线性的 - 与确切功能相似的两个重要点。我们认为,在自洽密度功能计算中,能量的密度驱动误差在密度误差中是二阶,并且大密度驱动的误差主要来自不正确的电子传输,而不是长度比原子直径大的尺度。

Delocalization errors, such as charge-transfer and some self-interaction errors, plague computationally-efficient and otherwise-accurate density functional approximations (DFAs). Evaluating a semi-local DFA non-self-consistently on the Hartree-Fock (HF) density is often recommended as a computationally cheap remedy for delocalization errors. For sophisticated meta-GGAs like SCAN, this approach can achieve remarkable accuracy. When this HF-DFT (or DFA@HF) significantly improves over the DFA, it is often presumed that the HF density is more accurate than the self-consistent DFA density. By applying the metrics of density-corrected density functional theory (DFT), we show that HF-DFT works for barrier heights by making a localizing charge transfer error or density over-correction, thereby producing a somewhat-reliable cancellation of density- and functional-driven errors for the energy. A quantitative analysis of the charge transfer errors in a few transition states confirms this trend. We do not have the exact functional and exact densities that are needed to evaluate the exact density- and functional-driven errors for the large BH76 database of barrier heights. Instead, we have identified and used three non-local proxy functionals (the SCAN 50% global hybrid, the range-separated hybrid LC-$ω$PBE, and SCAN-FLOSIC) and their self-consistent densities. These functionals yield reasonably accurate self-consistent barrier heights, and their self-consistent total energies are nearly piecewise linear in fractional electron number - two important points of similarity to the exact functional. We argue that density-driven errors of the energy in a self-consistent density functional calculation are second-order in the density error, and that large density-driven errors arise primarily from incorrect electron transfers over length scales larger than the diameter of an atom.

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