Systematic Study of the Basis Set Superposition Error in Core–Electron Correlation Effects

Phys. Chem. Chem. Phys.

Hansen

Bauer

et al. 2017

1,585

2,322

We present the GMTKN55 benchmark database for general main group thermochemistry, kinetics and noncovalent interactions. Compared to its popular predecessor GMTKN30 [Goerigk and Grimme J. Chem. Theory Comput., 2011, 7, 291], it allows assessment across a larger variety of chemical problems-with 13 new benchmark sets being presented for the first time-and it also provides reference values of significantly higher quality for most sets. GMTKN55 comprises 1505 relative energies based on 2462 single-point calculations and it is accessible to the user community via a dedicated website. Herein, we demonstrate the importance of better reference values, and we re-emphasise the need for London-dispersion corrections in density functional theory (DFT) treatments of thermochemical problems, including Minnesota methods. We assessed 217 variations of dispersion-corrected and -uncorrected density functional approximations, and carried out a detailed analysis of 83 of them to identify robust and reliable approaches. Double-hybrid functionals are the most reliable approaches for thermochemistry and noncovalent interactions, and they should be used whenever technically feasible. These are, in particular, DSD-BLYP-D3(BJ), DSD-PBEP86-D3(BJ), and B2GPPLYP-D3(BJ). The best hybrids are ωB97X-V, M052X-D3(0), and ωB97X-D3, but we also recommend PW6B95-D3(BJ) as the best conventional global hybrid. At the meta-generalised-gradient (meta-GGA) level, the SCAN-D3(BJ) method can be recommended. Other meta-GGAs are outperformed by the GGA functionals revPBE-D3(BJ), B97-D3(BJ), and OLYP-D3(BJ). We note that many popular methods, such as B3LYP, are not part of our recommendations. In fact, with our results we hope to inspire a change in the user community's perception of common DFT methods. We also encourage method developers to use GMTKN55 for cross-validation studies of new methodologies.

Section: Technical Detailsmentioning

confidence: 99%

A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions

Phys. Chem. Chem. Phys.

Hansen

Bauer

et al. 2017

1,585

2,322

“…The frozen-core approximation was used for all assessed double hybrids to prevent basis set superposition errors from core-core electron correlation. 60 The resolution of identity (RI) 61 approximation was used for the Coulomb integrals and for the PT2 correlation energy, utilizing the corresponding auxiliary basis sets in ORCA. We used the standalone DFT-D3 program 62…”

Section: Technical Detailsmentioning

confidence: 99%

An Analysis of Recent BLYP and PBE-Based Range-Separated Double-Hybrid Density Functional Approximations for Main-Group Thermochemistry, Kinetics and Noncovalent Interactions

Najibi¹,

Casanova-Páez²,

2021

Preprint

<div> <div> <div> <p>We investigate the effects of range separation of the exchange energy on electronic ground-state properties for recently published double-hybrid density functionals (DHDFs) with the extensive GMTKN55 database for general main-group thermochemistry, kinetics and noncovalent interactions. We include the semi-empirical range-separated DHDFs ωB2PLYP and ωB2GP-PLYP developed by our group for excitation energies, together with their ground-state-parametrized variants, which we denote herein as ωB2PLYP18 and ωB2GP-PLYP18. We also include the non-empirical range-separated DHDFs RSX-0DH and RSX-QIDH. For all six DHDFs, damping parameters for the DFT-D3 dispersion correction (and for its DFT-D4 variant) are presented. We comment on when the range-separated functionals can be more beneficial than their global counterparts, and conclude that range separation alone is no guarantee for overall improved results. We observe that the BLYP-based functionals generally outperform the PBE-based functionals. We finally note that the best-performing double-hybrid density functionals for GMTKN55 are still the semi-empirical range-separated double hybrids ωDSD3-PBEP86-D4 and ωDSD72-PBEP86-D4, the former of which includes a third-order perturbative correlation term in addition to the more conventional second- order perturbation that DHDFs are based upon.</p> </div> </div> </div>

“…All BLYP calculations were treated with the resolution of the identity (RI-J) approximation for Coulomb integrals and appropriate auxiliary basis sets, [62,63] while hybrid, doublehybrid, and MP2-type calculations were done with the combined resolution-of-the-identity for Coulomb and the chain-of-sphere approximations for exchange integrals (RIJCOSX). [64] We also used the frozen core approximation for the second-order perturbative steps of the DHDF and MP2-type calculations to prevent core-core BSSE, [65] as well as the RI approximation with appropriate auxiliary basis sets to speed up those steps. [63] All calculations were carried out with ORCA's quadrature grid '3', followed by a non-iterative step with the larger grid '4'.…”

Section: Computational Details Technical Detailsmentioning

confidence: 99%

Assessing the Applicability of the Geometric Counterpoise Correction in B2PLYP/Double-ζ Calculations for Thermochemistry, Kinetics, and Noncovalent Interactions

Mehta

2021

Aust. J. Chem.

We present a proof-of-concept study of the suitability of Kruse and Grimme's geometric counterpoise correction (gCP) for basis set superposition errors (BSSEs) in double-hybrid density functional calculations with a double-z basis set. The gCP approach only requires geometrical information as an input and no orbital/density information is needed. Therefore, this correction is practically free of any additional cost. gCP is trained against the Boys and Bernardi counterpoise correction across a set of 528 noncovalently bound dimers. We investigate the suitability of the approach for the B2PLYP/def2-SVP level of theory, and reveal error compensation effects-missing London dispersion and the BSSE-associated with B2PLYP/def2-SVP calculations, and present B2PLYP-gCP-D3(BJ)/def2-SVP with the reparametrised DFT-D3(BJ) and gCP corrections as a more balanced alternative. Benchmarking results on the S66x8 benchmark set for noncovalent interactions and the GMTKN55 database for main-group thermochemistry, kinetics, and noncovalent interactions show a statistical improvement of the B2PLYP-gCP-D3(BJ) scheme over plain B2PLYP and B2PLYP-D3(BJ). B2PLYP-D3(BJ) shows significant overestimation of interaction energies, barrier heights with larger deviations from the reference values, and wrong relative stabilities in conformers, all of which can be associated with BSSE. We find that the gCP-corrected method represents a significant improvement over B2PLYP-D3(BJ), particularly for intramolecular noncovalent interactions. These findings encourage future developments of efficient double-hybrid DFT strategies that can be applied when double-hybrid calculations with large basis sets are not feasible due to system size.