Measuring Density-Driven Errors Using Kohn–Sham Inversion
Measuring Density-Driven Errors Using Kohn–Sham Inversion
复制标题
使用 KohnâSham 反演测量密度驱动的误差
DOI：
10.1021/acs.jctc.0c00391
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发表时间：
2020
影响因子：
5.5
通讯作者：
and Burke, Kieron
中科院分区：
文献类型：
--
作者：
Nam, Seungsoo;Song, Suhwan;Sim, Eunji;and Burke, Kieron
Kohn-Sham（KS）反演，即在给定密度下找到精确的KS势，在局域基组中是困难的。我们研究了几种反演方案的精度和可靠性，发现密度驱动误差的估计在一个有用的精度水平。在密度驱动误差较大的典型情况下，Hartree-Fock密度泛函理论（HF-DFT）几乎与基于CCSD（T）密度的DFT一样精确。实际HF-DFT中的简单近似也使得误差比计算的密度驱动误差小得多。两个典型的例子，拉伸NaCl和HO·Cl-自由基，说明了HF-DFT是多么精确。
Kohn–Sham (KS) inversion, that is, the finding of the exact KS potential for a given density, is difficult in localized basis sets. We study the precision and reliability of several inversion schemes, finding estimates of density-driven errors at a useful level of accuracy. In typical cases of substantial density-driven errors, Hartree–Fock density functional theory (HF-DFT) is almost as accurate as DFT evaluated on CCSD(T) densities. A simple approximation in practical HF-DFT also makes errors much smaller than the density-driven errors being calculated. Two paradigm examples, stretched NaCl and the HO·Cl–radical, illustrate just how accurate HF-DFT is.