2018/02/16 by Diana N. Tahchieva, Tahchieva, D., Dirk Bakowies +5
Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Chemical Physics (physics.chem-ph) #Crystallography and molecular interactions #FOS: Physical sciences #Molecular Spectroscopy and Structure
paper · pdf · doi:10.48550/arxiv.1802.06033
openalex publication_date 2018/02/16 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
The reliability of popular density functionals was studied for the description of torsional profiles of 36 molecules: glyoxal, oxalyl halides and their thiocarbonyl derivatives. HF and \textcolorblackeighteen functionals of varying complexity, from local density to range-separated hybrid approximations and double-hybrid, 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 σ-hole based intermolecular binding in dimers and crystals.