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

By Narbe Mardirossian, M. Head‐Gordon. 2017

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ABSTRACT In the past 30 years, Kohn–Sham density functional theory has emerged as the most popular electronic structure method 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 non-empirical 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-L-D3. 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 self-interaction/delocalisation errors and/or strong correlation effects.

Subfields: Atomic and Molecular Physics, and Optics, Physical and Theoretical Chemistry, Spectroscopy

View Paper: https://www.semanticscholar.org/paper/fcc6c86324c81f1fdae595b3e3601e6e72c8ef9b

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Citations in the corpus

QUESTDB: A database of highly accurate excitation energies for the electronic structure community (2020, neutral): “[56] Mardirossian N, Head-Gordon M.”
Classical dynamical density functional theory: from fundamentals to applications (2020, neutral): “[80,623–626].”
Recent developments in libxc - A comprehensive library of functionals for density functional theory (2018, background): “In view of this, it is not surprising that hundreds of different approximations have been suggested over the past decades [7,8].”
Outsmarting Quantum Chemistry Through Transfer Learning (2018, methodology): “Density functional theory (DFT) 11–13 , perhaps the most popular QM method, is much faster than coupled cluster theory.”