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The CHAL336 Benchmark Set: How Well Do Quantum-Chemical Methods Describe Chalcogen-Bonding Interactions?

preprint
submitted on 05.01.2021, 07:11 and posted on 06.01.2021, 05:22 by Nisha Mehta, Thomas Fellowes, JONATHAN WHITE, Lars Goerigk

We present the CHAL336 benchmark set—the most comprehensive database for the assessment of chalcogen-bonding (CB) interactions. After careful selection of suitable systems and identification of three high-level reference methods, the set comprises 336 dimers each consisting of up to 49 atoms and covers both σ- and π-hole interactions across four categories: chalcogen-chalcogen, chalcogen-π, chalcogen-halogen, and chalcogen-nitrogen interactions. In a subsequent study of DFT methods, we re- emphasize the need for using proper London-dispersion corrections when treating noncovalent interactions. We also point out that the deterioration of results and systematic overestimation of interaction energies for some dispersion-corrected DFT methods does not hint at problems with the chosen dispersion correction, but is a consequence of large density-driven errors. We conclude this work by performing the most detailed DFT benchmark study for CB interactions to date. We assess 98 variations of dispersion- corrected and -uncorrected DFT methods, and carry out a detailed analysis of 72 of them. Double-hybrid functionals are the most reliable approaches for CB interactions, and they should be used whenever computationally feasible. The best three double hybrids are SOS0-PBE0-2-D3(BJ), revDSD-PBEP86-D3(BJ), and B2NCPLYP-D3(BJ). The best hybrids in this study are ωB97M-V, PW6B95-D3(0), and PW6B95-D3(BJ). We do not recommend using any lower-rung DFT methods nor the popular B3LYP and MP2 approaches, which have been used to describe CB interactions in the past. We hope to inspire a change in computational protocols surrounding CB interactions that leads away from the commonly used, popular methods to the more robust and accurate ones recommended herein. We would also like to encourage method developers to use our set for the investigation and reduction of density-driven errors in new density functional approximations.

Funding

Australian Research Council (DP180101413)

National Computational Infrastructure

Commonwealth Scientific and Industrial Research Organisation

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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

First versions of submitted manuscript and SI files

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