Standard grids for high‐precision integration of modern density functionals: SG‐2 and SG‐3

Dasgupta, Saswata; Herbert, John M.

doi:10.1002/jcc.24761

Cited by 121 publications

(125 citation statements)

References 41 publications

(86 reference statements)

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“…All electronic structure calculations were carried out using the PBE0 functional with the def2‐TZVPP basis set using the Gaussian, MOLPRO, and Q‐CHEM electronic structure program systems. SG‐3 or equivalent integration grids (e. g. Grid=UltraFine in Gaussian) were employed.…”

Section: Other Computational Detailsmentioning

confidence: 99%

The Atomic Partial Charges Arboretum: Trying to See the Forest for the Trees

et al. 2020

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Atomic partial charges are among the most commonly used interpretive tools in quantum chemistry. Dozens of different 'population analyses' are in use, which are best seen as proxies (indirect gauges) rather than measurements of a 'general ionicity'. For the GMTKN55 benchmark of nearly 2,500 maingroup molecules, which span a broad swathe of chemical space, some two dozen different charge distributions were evaluated at the PBE0 level near the 1-particle basis set limit. The correlation matrix between the different charge distributions exhibits a block structure; blocking is, broadly speaking, by charge distribution class. A principal component analysis on the entire dataset suggests that nearly all variation can be accounted for by just two 'principal components of ionicity': one has all the distributions going in sync, while the second corresponds mainly to Bader QTAIM vs. all others. A weaker third component corresponds to electrostatic charge models in opposition to the orbital-based ones. The single charge distributions that have the greatest statistical similarity to the first principal component are iterated Hirshfeld (Hirshfeld-I) and a minimal-basis projected modification of Bickelhaupt charges. If three individual variables, rather than three principal components, are to be identified that contain most of the information in the whole dataset, one representative for each of the three classes of Corminboeuf et al. is needed: one based on partitioning of the density (such as QTAIM), a second based on orbital partitioning (such as NPA), and a third based on the molecular electrostatic potential (such as HLY or CHELPG).

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Section: Other Computational Detailsmentioning

confidence: 99%

The Atomic Partial Charges Arboretum: Trying to See the Forest for the Trees

et al. 2020

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“…For nonbonded interactions, the use of a (99,590) grid is advised (although some meta-GGA functionals will require even finer grids for weakly bound complexes). Recently, pruned versions of the (75,302) and (99,590) grids (SG-2 and SG-3, respectively) were published [222], which should greatly expedite calculations with functionals that require fine grids.…”

Section: Effective Use Of Density Functionalsmentioning

confidence: 99%

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

2017

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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.

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“…The def2-mSVP basis set in the Karlsruhe def2 basis set family 30 is a modified version of def2-SV(P), which corrects for an overestimation of bond lengths involving hydrogen 31 . All DFT calculations used the SG-2 standard quadrature grid, which is of sufficient quality for B97-based functionals 32 .…”

Section: Reactant Optimizationmentioning

confidence: 99%

Reactants, Products, and Transition States of Elementary Chemical Reactions Based on Quantum Chemistry

Grambow¹,

Pattanaik²,

Green³

2020

Preprint

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Reaction times, activation energies, branching ratios, yields, and many other quantitative attributes are important for precise organic syntheses and generating detailed reaction mechanisms. Often, it would be useful to be able to classify proposed reactions as fast or slow. However, quantitative chemical reaction data, especially for atom-mapped reactions, are difficult to find in existing databases. Therefore, we used automated potential energy surface exploration to generate 12,000 organic reactions involving H, C, N, and O atoms calculated at the ωB97X-D3/def2-TZVP quantum chemistry level. We report the results of geometry optimizations and frequency calculations for reactants, products, and transition states of all reactions. Additionally, we extracted atom-mapped reaction SMILES, activation energies, and enthalpies of reaction. We believe that this data will accelerate progress in automated methods for organic synthesis and reaction mechanism generation-for example, by enabling the development of novel machine learning models for quantitative reaction prediction.

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Standard grids for high‐precision integration of modern density functionals: SG‐2 and SG‐3

Cited by 121 publications

References 41 publications

The Atomic Partial Charges Arboretum: Trying to See the Forest for the Trees

The Atomic Partial Charges Arboretum: Trying to See the Forest for the Trees

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

Reactants, Products, and Transition States of Elementary Chemical Reactions Based on Quantum Chemistry

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