期刊
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
卷 12, 期 2, 页码 800-807出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.0c03545
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资金
- Korean Research Foundation [NRF-2020R1A2C2007468, NRF-2020R1A4A1017737]
- NSF [CHEM 1856165]
- Rubicon project - Netherlands Organisation for Scientific Research (NWO) [019.181EN.026]
Fitting parameters in approximate density functionals often leads to errors from self-consistent densities and energy functionals being conflated. However, using density-corrected DFT can separate these errors. In some cases, using Hartree-Fock densities instead of self-consistent densities can provide more accurate results at no additional cost.
Empirical fitting of parameters in approximate density functionals is common. Such fits conflate errors in the self-consistent density with errors in the energy functional, but density-corrected DFT (DC-DFT) separates these two. We illustrate with catastrophic failures of a toy functional applied to H-2(+) at varying bond lengths, where the standard fitting procedure misses the exact functional; Grimme's D3 fit to noncovalent interactions, which can be contaminated by large density errors such as in the WATER27 and B30 data sets; and double-hybrids trained on self-consistent densities, which can perform poorly on systems with density-driven errors. In these cases, more accurate results are found at no additional cost by using Hartree-Fock (HF) densities instead of self-consistent densities. For binding energies of small water clusters, errors are greatly reduced. Range-separated hybrids with 100% HF at large distances suffer much less from this effect.
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