Torsional potentials of glyoxal, oxalyl halides and their thiocarbonyl derivatives: Challenges for DFT.
The reliability of popular density functionals was studied for the description of torsional profiles of 36 molecules: glyoxal, oxalyl halides and their thiocarbonyl derivatives. Sixteen functionals of varying complexity, from local density to range-separated hybrid approximations, have been considered and benchmarked against CCSD(T)-level rotational profiles. For molecules containing heavy halogens, all functionals except M05-2X and M06-2X fail to reproduce barrier heights accurately and a number of functionals introduce spurious minima. Dispersion corrections show no improvement. Calibrated torsion-corrected atom-centered potentials rectify the shortcomings of PBE and also improve on $\sigma$-hole based intermolecular binding in dimers and crystals.
Publisher URL: http://arxiv.org/abs/1802.06033
DOI: arXiv:1802.06033v1
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