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

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 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 self-interaction/delocalisation errors and/or strong correlation effects.