16OSTM10: A new open-shell transition metal conformational energies database to challenge contemporary semiempirical and force field methods

Arseniy Otlyotov; Andrey Moshchenkov; Luigi Cavallo; Yury Minenkov

doi:10.1039/d2cp01659a

16OSTM10: A new open-shell transition metal conformational energies database to challenge contemporary semiempirical and force field methods

Arseniy Otlyotov, Andrey Moshchenkov, Luigi Cavallo, Yury Minenkov

Research output: Contribution to journal › Article › peer-review

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Abstract

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.

Original language	English (US)
Journal	Physical Chemistry Chemical Physics
DOIs	https://doi.org/10.1039/d2cp01659a
State	Published - Jun 23 2022

Bibliographical note

KAUST 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

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1039/d2cp01659a

https://repository.kaust.edu.sa/bitstream/10754/679410/1/d2cp01659a_removed.pdf

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@article{b309bd2bda34415187604b90bc68f823,

title = "16OSTM10: A new open-shell transition metal conformational energies database to challenge contemporary semiempirical and force field methods",

abstract = "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.",

author = "Arseniy Otlyotov and Andrey Moshchenkov and Luigi Cavallo and Yury Minenkov",

note = "KAUST 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.",

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AU - Otlyotov, Arseniy

AU - Moshchenkov, Andrey

AU - Cavallo, Luigi

AU - Minenkov, Yury

N1 - KAUST 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.

PY - 2022/6/23

Y1 - 2022/6/23

N2 - 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.

AB - 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.

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SN - 1463-9076

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

ER -

16OSTM10: A new open-shell transition metal conformational energies database to challenge contemporary semiempirical and force field methods

Abstract

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