Show simple item record

dc.contributor.authorMinenkov, Yury
dc.contributor.authorSharapa, Dmitry I.
dc.contributor.authorCavallo, Luigi
dc.date.accessioned2018-05-29T11:09:55Z
dc.date.available2018-05-29T11:09:55Z
dc.date.issued2018-05-22
dc.identifier.citationMinenkov Y, Sharapa DI, Cavallo L (2018) Application of Semiempirical Methods to Transition Metal Complexes: Fast Results but Hard-to-Predict Accuracy. Journal of Chemical Theory and Computation. Available: http://dx.doi.org/10.1021/acs.jctc.8b00018.
dc.identifier.issn1549-9618
dc.identifier.issn1549-9626
dc.identifier.doi10.1021/acs.jctc.8b00018
dc.identifier.urihttp://hdl.handle.net/10754/627967
dc.description.abstractA series of semiempirical PM6* and PM7 methods has been tested in reproducing of relative conformational energies of 27 realistic-size complexes of 16 different transition metals (TMs). An analysis of relative energies derived from single-point energy evaluations on density functional theory (DFT) optimized conformers revealed pronounced deviations between semiempirical and DFT methods indicating fundamental difference in potential energy surfaces (PES). To identify the origin of the deviation, we compared fully optimized PM7 and respective DFT conformers. For many complexes, differences in PM7 and DFT conformational energies have been confirmed often manifesting themselves in false coordination of some atoms (H, O) to TMs and chemical transformations/distortion of coordination center geometry in PM7 structures. Despite geometry optimization with fixed coordination center geometry leads to some improvements in conformational energies, the resulting accuracy is still too low to recommend explored semiempirical methods for out-of-the-box conformational search/sampling: careful testing is always needed.
dc.description.sponsorshipWe gratefully acknowledge Prof. Frank Jensen, Department of Chemistry, Aarhus University, Denmark, Prof. J. J. P. Stewart, Stewart Computational Chemistry, Colorado Springs, USA and Dr. Alexander M. Genaev, N. N. Vorozhtsov Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia for helpful discussions. The research reported in this publication was supported by funding 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. Y.M. gratefully acknowledges support from the Government of the Russian Federation (Agreement № 074-02-2018-286).
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttps://pubs.acs.org/doi/10.1021/acs.jctc.8b00018
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jctc.8b00018.
dc.subjectConformational Sampling
dc.subjectDensity Functional Theory
dc.subjectTransition Metals
dc.subjectConformational Energies
dc.subjectSemiempirical Methods
dc.titleApplication of Semiempirical Methods to Transition Metal Complexes: Fast Results but Hard-to-Predict Accuracy.
dc.typeArticle
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Division
dc.contributor.departmentChemical Science Program
dc.identifier.journalJournal of Chemical Theory and Computation
dc.eprint.versionPost-print
dc.contributor.institutionMoscow Institute of Physics and Technology, Institutskiy Pereulok 9, Dolgoprudny, Moscow Region 141700, Russia
dc.contributor.institutionChair of Theoretical Chemistry and Interdisciplinary Center for Molecular Materials Friedrich-Alexander-Universität Erlangen-Nürnberg Egerlandstraße3, 91058 Erlangen, Germany
kaust.personMinenkov, Yury
kaust.personCavallo, Luigi


Files in this item

Thumbnail
Name:
acs.jctc.8b00018.pdf
Size:
606.6Kb
Format:
PDF
Description:
Accepted Manuscript
Embargo End Date:
2019-05-22

This item appears in the following Collection(s)

Show simple item record