Assessment of TD-DFT and LF-DFT for study of d - d transitions in first row transition metal hexaaqua complexes
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 tra...nsition 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.
Source:
Journal of Chemical Physics, 2015, 142, 21, 214111-Publisher:
- Amer Inst Physics, Melville
Funding / projects:
- Rational design and synthesis of biologically active and coordination compounds and functional materials, relevant for (bio)nanotechnology (RS-MESTD-Basic Research (BR or ON)-172035)
DOI: 10.1063/1.4922111
ISSN: 0021-9606
PubMed: 26049483
WoS: 000355931800067
Scopus: 2-s2.0-84930960280
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Institution/Community
IHTMTY - JOUR AU - Vlahović, Filip AU - Perić, Marko AU - Gruden-Pavlović, Maja AU - Zlatar, Matija PY - 2015 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/1658 AB - 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. PB - Amer Inst Physics, Melville T2 - Journal of Chemical Physics T1 - Assessment of TD-DFT and LF-DFT for study of d - d transitions in first row transition metal hexaaqua complexes VL - 142 IS - 21 SP - 214111 DO - 10.1063/1.4922111 ER -
@article{ author = "Vlahović, Filip and Perić, Marko and Gruden-Pavlović, Maja and Zlatar, Matija", year = "2015", 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.", publisher = "Amer Inst Physics, Melville", journal = "Journal of Chemical Physics", title = "Assessment of TD-DFT and LF-DFT for study of d - d transitions in first row transition metal hexaaqua complexes", volume = "142", number = "21", pages = "214111", doi = "10.1063/1.4922111" }
Vlahović, F., Perić, M., Gruden-Pavlović, M.,& Zlatar, M.. (2015). Assessment of TD-DFT and LF-DFT for study of d - d transitions in first row transition metal hexaaqua complexes. in Journal of Chemical Physics Amer Inst Physics, Melville., 142(21), 214111. https://doi.org/10.1063/1.4922111
Vlahović F, Perić M, Gruden-Pavlović M, Zlatar M. Assessment of TD-DFT and LF-DFT for study of d - d transitions in first row transition metal hexaaqua complexes. in Journal of Chemical Physics. 2015;142(21):214111. doi:10.1063/1.4922111 .
Vlahović, Filip, Perić, Marko, Gruden-Pavlović, Maja, Zlatar, Matija, "Assessment of TD-DFT and LF-DFT for study of d - d transitions in first row transition metal hexaaqua complexes" in Journal of Chemical Physics, 142, no. 21 (2015):214111, https://doi.org/10.1063/1.4922111 . .