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Measuring Density-Driven Errors Using Kohn–Sham Inversion

Cite this: J. Chem. Theory Comput. 2020, 16, 8, 5014–5023
Publication Date (Web):July 15, 2020
https://doi.org/10.1021/acs.jctc.0c00391
Copyright © 2020 American Chemical Society
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    Abstract

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    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.

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    • Inversion results of CCSD and CCSD(T) densities for NaCl and ZMP results for the HO·Cl– complex (PDF)

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