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Assessment of TD-DFT and LF-DFT for study of d - d transitions in first row transition metal hexaaqua complexes

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2015
tddftlfdft.pdf (1.174Mb)
Authors
Vlahović, Filip
Perić, Marko
Gruden-Pavlović, Maja
Zlatar, Matija
Article (Published version)
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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-172035)

DOI: 10.1063/1.4922111

ISSN: 0021-9606

PubMed: 26049483

WoS: 000355931800067

Scopus: 2-s2.0-84930960280
[ Google Scholar ]
28
22
URI
https://cer.ihtm.bg.ac.rs/handle/123456789/1658
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  • Radovi istraživača / Researchers' publications
Institution/Community
IHTM
TY  - 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 . .

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