Revised values for the X23 benchmark set of molecular crystals

Dolgonos, Grygoriy; Hoja, Johannes; Boese, A. Daniel

doi:10.1039/c9cp04488d

Cited by 48 publications

(118 citation statements)

References 85 publications

(97 reference statements)

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“…When comparing the results with the recently suggested, new, back-corrected reference values Elatt ref,exp for the X23 benchmark set [49], we obtained a MSE of -7.91 kJ/mol for PBE-D3 and -0.75 for B97-D, which correspond to 11.8 % and 7.7 %, respectively. Thus, comparing our results with the As for the relative deviations from the experiment, overall, B97-D follows the PBE-D3 pattern (see Figure 2), which shows the consistency of both approaches.…”

Section: Calculated Lattice Energies For the X23 Benchmark Setmentioning

confidence: 70%

“…Other studies report a lower MAE of 4.8 kJ/mol and 2.8 kJ/mol for the C21 [19,49] and 4.6 kJ/mol and 1.4 kJ/mol for the X23 set with PBE-D3 [17,49] depending on the exact choice of the reference values. The authors employed the plane-wave DFT program VASP using PAW-potentials and a very large basis with a cutoff of 1000 eV and tight convergence criteria.…”

Section: Calculated Lattice Energies For the X23 Benchmark Setmentioning

confidence: 95%

“…Dolgonos et al recently introduced new and revised reference values for the X23 benchmark set [49]. Experimental unit-cell volumes were back-corrected for thermal and zero-point energy effects, and now make it possible to directly compare the unit cell parameter optimizations from electronic structure calculations with their newly-introduced V ref el , which may serve as a reference for benchmarking volumes obtained via the minimization of electronic energies.…”

Section: Changes Of Unit Cell Volumes and Lattice Parametersmentioning

confidence: 99%

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Intermolecular Interactions in Molecular Organic Crystals upon Relaxation of Lattice Parameters

Stein

Heimsaat

2019

Crystals

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Crystal structure prediction is based on the assumption that the most thermodynamically stable structure will crystallize first. The existence of other structures such as polymorphs or from counterenantiomers requires an accurate calculation of the electronic energy. Using atom-centered Gaussian basis functions in periodic Density Functional Theory (DFT) calculations in Turbomole, the performance of two dispersion-corrected functionals, PBE-D3 and B97-D, is assessed for molecular organic crystals of the X23 benchmark set. B97-D shows a MAE (mean absolute error) of 4 kJ/mol, compared to 9 kJ/mol for PBE-D3. A strategy for the convergence of lattice energies towards the basis set limit is outlined. A simultaneous minimization of molecular structures and lattice parameters shows that both methods are able to reproduce experimental unit cell parameters to within 4–5%. Calculated lattice energies, however, deviate slightly more from the experiment, i.e., by 0.4 kJ/mol after unit cell optimization for PBE-D3 and 0.5 kJ/mol for B97-D. The accuracy of the calculated lattice energies compared to the experimental values demonstrates the ability of current DFT methods to assist in the quest for possible polymorphs and enantioselective crystallization processes.

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Section: Calculated Lattice Energies For the X23 Benchmark Setmentioning

confidence: 70%

Section: Calculated Lattice Energies For the X23 Benchmark Setmentioning

confidence: 95%

Section: Changes Of Unit Cell Volumes and Lattice Parametersmentioning

confidence: 99%

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Intermolecular Interactions in Molecular Organic Crystals upon Relaxation of Lattice Parameters

Stein

Heimsaat

2019

Crystals

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“…X23 and ICE10-The next benchmarks we consider are the X23 set of 23 organic crystals, for which Boese and co-workers very recently presented back-corrected references for lattice energies and volumes (X23b), 96 as well as the ICE10 set of 10 different ices. 97 For both of these sets, we concluded full optimizations at the r 2 SCAN-3c level to a convergence of 0.006 kcal/mol (10 −5 eH) with the fine k-point settings recommended in the original publications.…”

Section: E Metal-organic Reactionsmentioning

confidence: 99%

“…However, for the sake of comparability, we have used the original references of Boese and co-workers throughout this discussion. 96 For the molar volumes, Boese and coworkers provide back-corrections averaged over PBE-D3, BLYP-D3 and RPBE-D3 calculations. We noted that for several examples the RPBE values are unrealistically large, as also mentioned by the authors, 96 which leads to outliers in the comparison with all methods (cytosine 15% deviation, adamantane 10%).…”

Section: E Metal-organic Reactionsmentioning

confidence: 99%

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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Tuning the quasi‐harmonic treatment of crystalline ionic liquids within the density functional theory

Červinka

2021

J Comput Chem

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Five ionic liquids are selected for benchmarking the performance of quasi‐harmonic density functional theory (DFT) calculations of structural, phonon, and thermodynamic properties of their crystals. Data predicted by individual computational setups are sorted, establishing a distinct hierarchy among the first‐principles approaches. PBE‐D3 and B3LYP‐D3 functionals are coupled with various plane wave and Gaussian‐type orbital (GTO) basis sets. Propagation of the basis set superposition error and of the imperfections of both functionals into finite‐temperature properties is discussed in detail. PBE‐D3 together with a triple‐zeta GTO basis set often yields the most accurate predictions of predicted molar volume and heat capacity with errors at 1% and 8%, respectively, representing the state‐of‐the‐art for quasi‐harmonic DFT calculations for crystalline ionic liquids. Fortuitous error cancellation between the basis‐set superposition (overbinding) and PBE imperfection (overexpanding) strongly affects the overall accuracy, unlike the case of B3LYP/GTO calculations, impeding systematic convergence of the methodology towards higher accuracy.

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Revised values for the X23 benchmark set of molecular crystals

Abstract: A revised reference value set for molecular crystals: X23b; new cell volumes and lattice energies including volumetric expansion due to zero-point energy and thermal effects.

Cited by 48 publications

References 85 publications

Intermolecular Interactions in Molecular Organic Crystals upon Relaxation of Lattice Parameters

Intermolecular Interactions in Molecular Organic Crystals upon Relaxation of Lattice Parameters

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

Tuning the quasi‐harmonic treatment of crystalline ionic liquids within the density functional theory

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