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Torsional potentials of glyoxal, oxalyl halides and their thiocarbonyl derivatives: Challenges for DFT

Tahchieva, D. and Bakowies, D. and Ramakrishnan, R. and von Lilienfeld, O. A.. (2018) Torsional potentials of glyoxal, oxalyl halides and their thiocarbonyl derivatives: Challenges for DFT. Journal of chemical theory and computation. pp. 1-11.

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Abstract

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 σ-hole based intermolecular binding in dimers and crystals.
Faculties and Departments:05 Faculty of Science > Departement Chemie
05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Lilienfeld)
UniBasel Contributors:Tahchieva, Diana and Bakowies, Dirk and Ramakrishnan, Raghunathan and von Lilienfeld, Anatole
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
ISSN:1549-9618
e-ISSN:1549-9626
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
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Last Modified:31 Jul 2019 07:43
Deposited On:31 Jul 2019 07:43

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