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-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 selfinteraction/delocalisation errors and/or strong correlation effects.

An assessment of strategies for the development of solid-state adsorbents for vehicular hydrogen storage

“…70 The root-mean-square errors of molecular interaction energies from some widely used functionals across a Table 4. 48 It is evident that the width of the distribution of errors roughly reduces by a factor of two from the standard ÀD corrections to the best available methods. Nevertheless, although improving quantitative accuracy remains the goal of DFT XC functional development, it is worth emphasizing that qualitative trends in binding energy are often reproduced even with comparatively simple functionals, including generalized gradient approximations (GGAs) with standard ÀD corrections.…”

“…[47][48][49][50] Each method offers different strengths in computational accuracy, expense, and model complexity.…”

“…Density functional theory [47][48][49][50] is the predominant electronic structure method for modeling gas interactions with complex systems because it offers a favorable trade-off between binding energy accuracy and computational cost. The exchange-correlation (XC) contribution to the energy is the only parameter that cannot be evaluated exactly and instead must be treated by XC density functional approximations.…”

Molecular excited states from the SCAN functional

“…There have also been a limited number of assessments of the functional applied to molecular systems [9][10][11][12], focusing on ground state properties, where there are again indications that it does not behave as a prototypical semi-local functional. In particular, observations around its hybrid-like performance for an extensive set of atomisation energies and related ground state properties [13], are indicative of the SCAN functional reproducing aspects of the underlying behaviour attributed to global hybrid functionals.…”

Local resonances in STM manipulation of chlorobenzene on Si(111)-7×7: performance of different cluster models and density functionals

“…However, such couplings are a requirement for a resonance model to describe the STM-induced desorption (see below). Also, other functionals, such as M06, M062X, PBE0, CAM-B3LYP and BP86 were tested, but no relevant differences were found [39][40][41][42][43]. For a recent general assessment of the performance of DFT functionals see Refs.…”