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Assessment of TD-DFT and LF-DFT for study of d - d transitions in first row transition metal hexaaqua complexes
dc.creator | Vlahović, Filip | |
dc.creator | Perić, Marko | |
dc.creator | Gruden-Pavlović, Maja | |
dc.creator | Zlatar, Matija | |
dc.date.accessioned | 2019-01-30T17:44:15Z | |
dc.date.available | 2019-01-30T17:44:15Z | |
dc.date.issued | 2015 | |
dc.identifier.issn | 0021-9606 | |
dc.identifier.uri | https://cer.ihtm.bg.ac.rs/handle/123456789/1658 | |
dc.description.abstract | Herein, 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. | en |
dc.publisher | Amer Inst Physics, Melville | |
dc.relation | info:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172035/RS// | |
dc.rights | openAccess | |
dc.source | Journal of Chemical Physics | |
dc.title | Assessment of TD-DFT and LF-DFT for study of d - d transitions in first row transition metal hexaaqua complexes | en |
dc.type | article | |
dc.rights.license | ARR | |
dcterms.abstract | Влаховиц, Филип; Златар, Матија; Периц, Марко; Груден-Павловић, Маја; | |
dc.citation.volume | 142 | |
dc.citation.issue | 21 | |
dc.citation.spage | 214111 | |
dc.citation.other | 142(21): | |
dc.citation.rank | M21 | |
dc.identifier.pmid | 26049483 | |
dc.identifier.doi | 10.1063/1.4922111 | |
dc.identifier.fulltext | https://cer.ihtm.bg.ac.rs//bitstream/id/6306/tddftlfdft.pdf | |
dc.identifier.scopus | 2-s2.0-84930960280 | |
dc.identifier.wos | 000355931800067 | |
dc.type.version | publishedVersion |