Density sensitivity of empirical functionals

2020/08/04 by Suhwan Song, Song, Suhwan, Stefan Vuckovic +5
Chemistry · Materials Science · Physics and Astronomy · #Advanced Chemical Physics Studies #Advanced NMR Techniques and Applications #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Machine Learning in Materials Science

paper · pdf · doi:10.48550/arxiv.2008.01261

openalex publication_date 2020/08/04 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28

Abstract

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 datasets; 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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