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

preprint
submitted on 22.03.2021, 04:41 and posted on 23.03.2021, 10:09 by Asim Najibi, Marcos Casanova Paez, Lars Goerigk

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.

Funding

National Computational Merit Allocation Scheme (project fk5)

History

Email Address of Submitting Author

lars.goerigk@unimelb.edu.au

Institution

The University of Melbourne

Country

Australia

ORCID For Submitting Author

0000-0003-3155-675X

Declaration of Conflict of Interest

No conflict of interest

Version Notes

Version 1, under peer-review

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