The new database, 16OSTM10, containing 10 conformations for each of 16 non-multireference realistic-size open-shell transition metal (OSTM) complexes has been developed. Contemporary composite density functional theory (DFT) (PBEh3c, B97-3c), semiempirical (PM6, PM7) and the methods of GFNn-xTB/FF family were examined against conventional DFT (PBE-D3(BJ), PBE0-D3(BJ), M06 and ωB97X-V) to reproduce the conformational energies. While a good performance is observed for the conventional (average Pearson correlation coefficient is ρ = 0.91) and composite DFT (average ρ = 0.93), semiempirical and force-field methods should be still used with a caution for these challenging compounds. The corresponding average ρ values are 0.53 (PM6, PM7), 0.75 (GFN1-xTB, GFN2-xTB) and 0.62 (GFN-FF). Accounting for the intramolecular dispersion interactions turned out to be crucial for 4 OSTM complexes bearing bulky substituents in the close proximity to each other. The influence of the scalar relativistic effects on the conformational energies is negligible for the considered 3d metal species.
Bibliographical noteKAUST Repository Item: Exported on 2022-06-29
Acknowledgements: This work was financially supported by the grant of the President of the Russian Federation ("The development of an efficient approach for prediction of the properties of the openshell organometallic compounds", project МК-176.2022.1.3). L. C. gratefully acknowledges the financial support from King Abdullah University of Science and Technology (KAUST). For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science and Technology (KAUST) in Thuwal, Saudi Arabia and the Joint Supercomputer Center of RAS in Moscow, Russia.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry