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

Abstract

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 109 variations of dispersion-corrected and -uncorrected DFT methods, and carry out a detailed analysis of 80 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 the popular B3LYP functional nor the MP2 approach, which have both been frequently 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. File list (5) download file view on ChemRxiv CHAL336.pdf (3.01 MiB) download file view on ChemRxiv CHAL336_SI_part1.pdf (1.01 MiB) download file view on ChemRxiv CHAL336_SI_part2_structures.zip (1.95 MiB) download file view on ChemRxiv CHAL336_SI_part3_refvalues.zip (78.17 KiB) download file view on ChemRxiv CHAL336_SI_part4_DFTMP2data.zip (0.90 MiB)

Exploring Avenues beyond Revised DSD Functionals: I. Range Separation, with xDSD as a Special Case

“…These 336 dimer interaction energies can be subdivided into four categories: chalcogen–chalcogen, chalcogen−π, chalcogen–halogen, and chalcogen–nitrogen interactions. Mehta et al have already assessed the performance of a large number of DFT methods (see Figure 9 of their article 90 ), and our revDSD-PBEP86-D3BJ 9 was among the best three performers (the differences between these are arguably a photo finish). Here, we evaluate the performance for CHAL336 of eight selected functionals, namely, x DSD 75 -PBEP86-D3BJ (D4), x DOD 72 -PBEP86-D3BJ (D4), ωDSD 72 -PBEP86-D3BJ (D4), and ωDOD 72 -PBEP86-D3BJ (D4).…”

“…These four test sets are MOBH35, originally proposed by Iron and Janes, 88 POLYPYR21, MPCONF196, 89 and CHAL336. 90 …”

“…While the present article was in peer review, Mehta et al ( 90 ) proposed a comprehensive database of chalcogen bonding interactions, CHAL336. Consisting of molecules up to 49 atoms, CHAL336 contains 336 dimers, and a complete evaluation requires 1008 single-point energy calculations.…”

“…Here, we evaluate the performance for CHAL336 of eight selected functionals, namely, x DSD 75 -PBEP86-D3BJ (D4), x DOD 72 -PBEP86-D3BJ (D4), ωDSD 72 -PBEP86-D3BJ (D4), and ωDOD 72 -PBEP86-D3BJ (D4). While we were at it, we also tested revDSD-PBEP86-D3BJ and revDSD-PBEP86-D4, the former to check the consistency with ref ( 90 ) and the latter as the D4 variant had not been included in ref ( 90 ).…”

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

“…Although the BB-CP and gCP corrections were developed as independent procedures, London dispersion corrections play an important role in the DFT-based treatment of geometries, thermochemistry, kinetics, and noncovalent interactions. [29,35,71,72,133,[137][138][139][140][141][142][143][144][145][146] Herein, we will study in detail if a refit of the DFT-D3(BJ) parameters has any positive effects. We find a significant improvement in performance when the DFT-D3(BJ) parameters s 8 , a 1 , and a 2 in Eqn 6 are re-determined in the presence of the BB-CP correction with the procedure discussed earlier.…”