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

We present the CHAL336 benchmark set-the most comprehensive database for assessment of chalcogen-bonding (CB) interactions. After careful selection suitable systems and identification three high-level reference methods, set comprises 336 dimers each consisting up to 49 atoms covers both σ- π-hole interactions across four categories: chalcogen-chalcogen, chalcogen-π, chalcogen-halogen, chalcogen-nitrogen In a subsequent study DFT we re-emphasize need using proper London dispersion corrections when treating noncovalent also point out that deterioration results systematic overestimation interaction energies some dispersion-corrected methods does not hint at problems with chosen correction but is consequence large density-driven errors. conclude this work by performing detailed CB date. assess 109 variations dispersion-uncorrected carry analysis 80 them. Double-hybrid functionals are reliable approaches interactions, they should be used whenever computationally feasible. The best double hybrids SOS0-PBE0-2-D3(BJ), revDSD-PBEP86-D3(BJ), B2NCPLYP-D3(BJ). in ωB97M-V, PW6B95-D3(0), PW6B95-D3(BJ). do recommend popular B3LYP functional nor MP2 approach, which have been frequently describe past. hope inspire change computational protocols surrounding leads away from commonly used, more robust accurate ones recommended herein. would like encourage method developers use our investigation reduction errors new density approximations.