Extension and evaluation of the D4 London-dispersion model for periodic systems

Caldeweyher, Eike; Mewes, Jan‐Michael; Ehlert, Sebastian; Grimme, Stefan

doi:10.1039/d0cp00502a

Cited by 263 publications

(219 citation statements)

References 94 publications

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“…In line with a presence of SIE, all dispersion-inclusive methods considered here and in a recent survey significantly overestimate the interaction of CO with MgO and to a lesser extend also that of C 2 H 2 with NaCl. 94 SCAN-rVV10 significantly overbinds CO to the MgO surface with an adsorption energy of 8.1 kcal/mol (+62%), and similarly for C 2 H 2 on NaCl with 8.8 kcal/mol (+54%). Although dispersion-uncorrected SCAN is closer to the experiment with 6.0 kcal/mol and 6.5 kcal/mol, this is clearly a result of error-compensation between SIE and the lack of long-range dispersion.…”

Section: G Adsorption On Polar and Non-polar Surfacesmentioning

confidence: 97%

“…A recent survey of dispersion-corrected plane-wave DFT with various DFAs and dispersion corrections has shown PBE0-D4 to be most accurate and robust with an outstanding MD and RMSD of only 0.2 and 0.5 kcal/mol, respectively. 94 The best (m)GGAs were TPSS-D4 and revPBE-D4, both with an RMSD of 0.6 kcal/mol. SCAN, which has been considered in combination with the D4 and rVV10 dispersion corrections provided a very consistent description (i.e., the smallest relative errors between chemically similar systems), but a sizable RMSD of 1.2 kcal/mol due to a consistent overbinding (MD = −0.7 kcal/mol).…”

Section: E Metal-organic Reactionsmentioning

confidence: 99%

“…These optimizations relax the first (complete) layer of the surface as well as the adsorbate. For benzene on Au, we use the structure from a previous work 94 as the starting point, while the initial structures for Ag and Cu are generated by uniformly scaling the cellsize of the Au case to match the lattice parameters of Cu and Ag. Further calculations for the composite methods r 2 SCAN-3c and B97-3c, as well as with the DFAs PBE-D4, BLYP-D4, and M06L-D4 are conducted with Riper in a 2-D periodic 5×5 k-point grid, and employ the mTZVPP basis set with def2-ECPs for Ag and Au, as well as the gCP correction.…”

Section: G Adsorption On Polar and Non-polar Surfacesmentioning

confidence: 99%

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r2SCAN-3c: An Efficient “Swiss Army Knife” Composite Electronic-Structure Method

Hansen¹,

Ehlert²,

Mewes³

2020

Preprint

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The recently proposed second revision of the SCAN meta-GGA density-functional approximation (DFA) {Furness et al., J. Phys. Chem. Lett. 2020, 11, 8208-8215, termed r2SCAN} is used to construct an efficient composite electronic-structure method termed r2SCAN-3c, expanding the "3c'' series (hybrid: HSE/PBEh-3c, GGA: B97-3c, HF: HF-3c) to themGGA level. To this end, the unaltered r2SCAN functional is combined with a tailor-made triple-zeta Gaussian AO-basis as well as with refitted D4 and gCP corrections for London-dispersion and basis-set superposition error. The performance of the new method is evaluated for the GMTKN55 thermochemical database covering large parts of chemical space with about 1500 data points, as well as additional benchmarks for noncovalent interactions, organometallic reactions, lattice energies of organic molecules and ices, as well as for the adsorption on polar salt and non-polar coinage-metal surfaces. These comprehensive tests reveal a spectacular performance and robustness of r2SCAN-3c for reaction energies and noncovalent interactions in molecular and periodic systems, as well as outstanding conformational energies, and consistent structures. At just one tenth of the cost, r2SCAN-3c provides one of the best results of all semi-local DFT/QZ methods ever tested for the GMTKN55 benchmark database. Specifically for reaction and conformational energies as well as for noncovalent interactions, the new method outperforms hybrid-DFT/QZ approaches, compared to which the computational savings are even larger (factor 100-1000). In relation to other "3c'' methods, r2SCAN-3c by far surpasses the accuracy of its predecessor B97-3c at only about twice the cost. The perhaps most relevant remaining systematic deviation of r2SCAN-3c is due to self-interaction-error, owing to its mGGA nature. However, SIE is notably reduced compared to other (m)GGAs, as is demonstrated for several examples. After all, this remarkably efficient and robust method is chosen as our new group default, replacing previous low-level DFT and partially even expensive high-level methods in most standard applications for systems with up to several hundreds of atoms.

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Section: G Adsorption On Polar and Non-polar Surfacesmentioning

confidence: 97%

Section: E Metal-organic Reactionsmentioning

confidence: 99%

Section: G Adsorption On Polar and Non-polar Surfacesmentioning

confidence: 99%

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r2SCAN-3c: An Efficient “Swiss Army Knife” Composite Electronic-Structure Method

Hansen¹,

Ehlert²,

Mewes³

2020

Preprint

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“…75 According to many tests on neutral organic systems, DFT-D3 and DFT-D4 methods provide both accurate asymptotic dispersion energies of roughly coupled-cluster accuracy 21 while D4 is somewhat superior for ionic or metallic cases. 69,76 If this also holds for the important class of ion-π complexes is one of the main questions of the present work. Due to the high computational efficiency of the additive DFT-D schemes, they are also suitable for low-cost methods including force-fields.…”

Section: Semi-classical London Dispersion Correctionsmentioning

confidence: 89%

Benchmarking London dispersion corrected density functional theory for noncovalent ion-pi interactions

Spicher¹,

Caldeweyher

Hansen³

2021

Preprint

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The strongly attractive non-covalent interactions of charged atoms or molecules with pi-systems are important bonding motifs in many chemical and biological systems. These so-called ion-pi interactions play a major role in enzymes, molecular recognition, and for the structure of proteins. To model ion-pi interactions with DFT, it is crucialto include London dispersion interactions, whose importance for ion-pi interactions is often underestimated. In this work, several dispersion-corrected DFT methods are evaluated for inter- and intramolecular anionic- and anion-pi interactions in larger and practically relevant molecules. We compare the DFT results with MP2, while highlyaccurate (local) coupled cluster values are provided as reference. The latter can also be a great help in the development and validation of approximate methods. We demonstrate that dispersion-uncorrected DFT underestimates ion-pi interactions significantly, even though electrostatic interactions dominate the overall binding. Accordingly, thenew charge dependent D4 dispersion model is found to be consistently better than the standard D3 correction. Dispersion-corrected DFT clearly outperforms MP2/CBS whereby the best performers come close to the accuracy limit of the reference values at considerably smaller computational cost. Due to its low cost, D4 can be combinedvery well with semi-empirical QM and force field methods, which is important in the development of more accurate methods for modeling large (bio)chemical systems (e.g. proteins). Another important aspect in modeling these charged systems with DFT is the self-interaction error (SIE). However, we do not find it to constitute a significant problem. Overall, the double hybrid PWPB95-D4/QZ turned out to be the most reliable among all assessed methods in predicting ion-pi interactions, which opens up new perspectives for systems where coupled cluster calculations are no longer computationally feasible.

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“…All quantum chemical calculations were performed by the GFN2-XTB method using the XTB 6.4.0 soware package. [65][66][67][68][69] The GFN2-XTB method, like the DFTB methods, is based on density functional theory. DFTB methods include pairwise empirical parameterization, while GFNn-XTB methods include empirical parameterization for individual atoms, which is a crucial advantage of the latter over DFTB methods.…”

Section: Computational Detailsmentioning

confidence: 99%

Deep neural network analysis of nanoparticle ordering to identify defects in layered carbon materials

et al. 2021

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Extension and evaluation of the D4 London-dispersion model for periodic systems

Abstract: We present an extension of the DFT-D4 model [J. Chem. Phys., 2019, 150, 154122] for periodic systems.

Cited by 263 publications

References 94 publications

r2SCAN-3c: An Efficient “Swiss Army Knife” Composite Electronic-Structure Method

r2SCAN-3c: An Efficient “Swiss Army Knife” Composite Electronic-Structure Method

Benchmarking London dispersion corrected density functional theory for noncovalent ion-pi interactions

Deep neural network analysis of nanoparticle ordering to identify defects in layered carbon materials

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