Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals

2017/06/21 by Narbe Mardirossian, Martin Head-Gordon, Martin Head‐Gordon · 2,334 citations
Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Chemistry #Computational chemistry #Density functional theory #History and advancements in chemistry #Molecular spectroscopy and chirality #Orbital-free density functional theory #Physics #Statistical physics #Theoretical physics #Time-dependent density functional theory

paper · open access · doi:10.1080/00268976.2017.1333644

published in Molecular Physics 115(19), 2315-2372 (Taylor & Francis)

openalex publication_date 2017/06/21 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

Abstract

In the past 30 years, Kohn–Sham density functional theory has emerged as the most popular electronic structuremethod in computational chemistry. To assess the ever-increasing number of approximate exchange-correlation functionals, this review benchmarks a total of 200 density functionals on a molecular database (MGCDB84) of nearly 5000 data points. The database employed, provided as Supplemental Data, is comprised of 84 data-sets and contains non-covalent interactions, isomerisation energies, thermochemistry, and barrier heights. In addition, the evolution of nonempirical and semi-empirical density functional design is reviewed, and guidelines are provided for the proper and effective use of density functionals. The most promising functional considered is ωB97M-V, a range-separated hybrid meta-GGA with VV10 nonlocal correlation, designed using a combinatorial approach. From the local GGAs, B97-D3, revPBE-D3, and BLYP-D3 are recommended, while from the local meta-GGAs, B97M-rV is the leading choice, followed by MS1-D3 and M06-LD3. The best hybrid GGAs are ωB97X-V, ωB97X-D3, and ωB97X-D, while useful hybrid meta-GGAs (besides ωB97M-V) include ωM05-D, M06-2X-D3, and MN15. Ultimately, today’s state-of-the-art functionals are close to achieving the level of accuracy desired for a broad range of chemical applications, and the principal remaining limitations are associated with systems that exhibit significant selfinteraction/ delocalisation errors and/or strong correlation effects.

Citations

• A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
• ωB97M-V: A combinatorially optimized, range-separated hybrid, meta-GGA density functional with VV10 nonlocal correlation
• Density functional theory is straying from the path toward the exact functional

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