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dc.creatorVlahović, Filip
dc.creatorPerić, Marko
dc.creatorGruden-Pavlović, Maja
dc.creatorZlatar, Matija
dc.date.accessioned2018-11-22T00:31:40Z
dc.date.available2018-11-22T00:31:40Z
dc.date.issued2015
dc.identifier.issn0021-9606
dc.identifier.urihttp://cherry.chem.bg.ac.rs/handle/123456789/1722
dc.description.abstractHerein, we present the systematic, comparative computational study of the d - d transitions in a series of first row transition metal hexaaqua complexes, [M(H2O)(6)](n+) (M2+/3+ = V2+/3+, Cr2+/3+, Mn2+/3+, Fe2+/3+, Co2+/3+, Ni2+) by the means of Time-dependent Density Functional Theory (TD-DFT) and Ligand Field Density Functional Theory (LF-DFT). Influence of various exchange-correlation (XC) approximations have been studied, and results have been compared to the experimental transition energies, as well as, to the previous high-level ab initio calculations. TD-DFT gives satisfactory results in the cases of d(2), d(4), and low-spin d(6) complexes, but fails in the cases when transitions depend only on the ligand field splitting, and for states with strong character of double excitation. LF-DFT, as a non-empirical approach to the ligand field theory, takes into account in a balanced way both dynamic and non-dynamic correlation effects and hence accurately describes the multiplets of transition metal complexes, even in difficult cases such as sextet-quartet splitting in d(5) complexes. Use of the XC functionals designed for the accurate description of the spin-state splitting, e.g., OPBE, OPBE0, or SSB-D, is found to be crucial for proper prediction of the spin-forbidden excitations by LF-DFT. It is shown that LF-DFT is a valuable alternative to both TD-DFT and ab initio methods. (C) 2015 AIP Publishing LLC.en
dc.publisherAmer Inst Physics, Melville
dc.relationinfo:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172035/RS//
dc.rightsrestrictedAccess
dc.sourceJournal of Chemical Physics
dc.titleAssessment of TD-DFT and LF-DFT for study of d - d transitions in first row transition metal hexaaqua complexesen
dc.typearticle
dc.rights.licenseARR
dcterms.abstractЗлатар, Матија; Влаховић, Филип; Периц, Марко; Груден-Павловић, Маја;
dc.citation.volume142
dc.citation.issue21
dc.identifier.wos000355931800067
dc.identifier.doi10.1063/1.4922111
dc.citation.other142(21):
dc.citation.rankM21
dc.identifier.pmid26049483
dc.description.otherSupplementary material: [http://cherry.chem.bg.ac.rs/handle/123456789/3341]
dc.type.versionpublishedVersion
dc.identifier.scopus2-s2.0-84930960280
dc.identifier.rcubKon_2868


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