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dc.creatorVujović, M.
dc.creatorHuynh, M.
dc.creatorSteiner, S.
dc.creatorGarcia-Fernandez, Pablo
dc.creatorElstner, Marcus
dc.creatorCui, Qiang
dc.creatorGruden-Pavlović, Maja
dc.date.accessioned2018-11-22T00:42:51Z
dc.date.available2018-11-22T00:42:51Z
dc.date.issued2019
dc.identifier.issn0192-8651
dc.identifier.urihttp://cherry.chem.bg.ac.rs/handle/123456789/353
dc.description.abstractIn this work, we explore the applicability and limitations of the current third order density functional tight binding (DFTB3) formalism for treating transition metal ions using nickel as an example. To be consistent with recent parameterization of DFTB3 for copper, the parametrization for nickel is conducted in a spin-polarized formulation and with orbital-resolved Hubbard parameters and their charge derivatives. The performance of the current parameter set is evaluated based on structural and energetic properties of a set of nickel-containing compounds that involve biologically relevant ligands. Qualitatively similar to findings in previous studies of copper complexes, the DFTB3 results are more reliable for nickel complexes with neutral ligands than for charged ligands; nevertheless, encouraging agreement is noted in comparison to the reference method, B3LYP/aug-cc-pVTZ, especially for structural properties, including cases that exhibit Jahn–Teller distortions; the structures also compare favorably to available X-ray data in the Cambridge Crystallographic Database for a number of nickel-containing compounds. As to limitations, we find it is necessary to use different d shell Hubbard charge derivatives for Ni(I) and Ni(II), due to the distinct electronic configurations for the nickel ion in the respective complexes, and substantial errors are observed for ligand binding energies, especially for charged ligands, d orbital splitting energies and splitting between singlet and triplet spin states for Ni(II) compounds. These observations highlight that future improvement in intra-d correlation and ligand polarization is required to enable the application of the DFTB3 model to complex transition metal ions. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.en
dc.relationinfo:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172035/RS//
dc.rightsrestrictedAccess
dc.sourceJournal of Computational Chemistry
dc.subjectDFTen
dc.subjectDFTB3en
dc.subjectHubbard parametersen
dc.subjectJahn–Teller distortionen
dc.subjectnickelen
dc.subjectspin statesen
dc.titleExploring the applicability of density functional tight binding to transition metal ions. Parameterization for nickel with the spin-polarized DFTB3 modelen
dc.typearticle
dc.rights.licenseARR
dcterms.abstractХуyнх, М.; Вујовић, М.; Елстнер, М.; Груден-Павловић, Маја; Гарциа-Фернандез, П.; Стеинер, С.; Цуи, Q.;
dc.citation.volume40
dc.citation.spage400
dc.citation.epage413
dc.identifier.wos000453013500012
dc.identifier.doi10.1002/jcc.25614
dc.citation.rankM22~
dc.type.versionpublishedVersionen
dc.identifier.scopus2-s2.0-85054695193
dc.identifier.rcubKon_1324


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