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 H2+ 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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Explaining and Fixing DFT Failures for Torsional Barrier
Most torsional barriers are predicted with high accuracies (about 1 kJ/mol) by standard semilocal functionals, but a small subset was found to have much larger errors. We created a database of almost 300 carbon–carbon torsional barriers, including 12 poorly behaved barriers, that stem from the Y═C—X group, where Y is O or S and X is a halide. Functionals with enhanced exchange mixing (about 50%) worked well for all barriers. We found that poor actors have delocalization errors caused by hyperconjugation. These problematic calculations are density-sensitive (i.e., DFT predictions change noticeably with the density), and using HF densities (HF-DFT) fixes these issues. For example, conventional B3LYP performs as accurately as exchange-enhanced functionals if the HF density is used. For long-chain conjugated molecules, HF-DFT can be much better than exchange-enhanced functionals. We suggest that HF-PBE0 has the best overall performance.
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- Award ID(s):
- 1856165
- PAR ID:
- 10220443
- Date Published:
- Journal Name:
- The journal of physical chemistry letters
- Issue:
- 12
- ISSN:
- 1948-7185
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.doi.102110.1021/acs.jpclett.1c00426
