Density functional theory (DFT) calculations have been completed for five Ni(II) complexes formed by polidentate peptide ligands to predict the electronic absorption spectrum. The ligands examined were glycyl-glycyl-glycine (abbreviated as GGG), glycyl-glycyl-glycyl-glycine (GGGG), glycyl-glycyl-histidine (GGH), glycyl-glycyl-cysteine (GGC) and triethylenetetramine (trien). Thirteen functionals (B3LYP, B3P86, CAM-B3LYP, ω-B97x-D, MPW1PW91, HSE06, PBE0, BHandHLYP, TPSSh, M06, M06-2X, BLYP and PBE) and two basis sets (LANL2DZ and def2-TZVP) were tested. On the basis of the mean absolute percent deviation (MAPD) the following ranking among the functionals was found: HSE06 ~ MPW1PW91 ~ PBE0 > ω-B97x-D ~ B3P86 ~ B3LYP ~ CAM-B3LYP > TPSSh > PBE ~ BLYP ~ BHandHLYP >> M06 >> M06-2X. Concerning the basis sets, the triple-ζ def2-TZVP performs better than the double-ζ LANL2DZ. With the functional HSE06 and the basis set def2-TZVP the MAPD with respect to the experimental λmax values is 1.59% with a standard deviation of 1.17%. The absorption electronic spectra were interpreted in terms of vertical excitations between occupied and virtual MOs based on Ni-d atomic orbitals. The electronic structure of the Ni(II) species was finally calculated and discussed.
Accurate prediction of vertical electronic transitions of Ni(II) coordination compounds via time dependent density functional theory / Sciortino, Giuseppe; Lihi, Norbert; Czine, Tamás; Maréchal, Jean-Didier; Lledós, Agustí; Garribba, Eugenio. - In: INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY. - ISSN 0020-7608. - (2018), p. e25655. [10.1002/qua.25655]
Accurate prediction of vertical electronic transitions of Ni(II) coordination compounds via time dependent density functional theory
Garribba, Eugenio
2018-01-01
Abstract
Density functional theory (DFT) calculations have been completed for five Ni(II) complexes formed by polidentate peptide ligands to predict the electronic absorption spectrum. The ligands examined were glycyl-glycyl-glycine (abbreviated as GGG), glycyl-glycyl-glycyl-glycine (GGGG), glycyl-glycyl-histidine (GGH), glycyl-glycyl-cysteine (GGC) and triethylenetetramine (trien). Thirteen functionals (B3LYP, B3P86, CAM-B3LYP, ω-B97x-D, MPW1PW91, HSE06, PBE0, BHandHLYP, TPSSh, M06, M06-2X, BLYP and PBE) and two basis sets (LANL2DZ and def2-TZVP) were tested. On the basis of the mean absolute percent deviation (MAPD) the following ranking among the functionals was found: HSE06 ~ MPW1PW91 ~ PBE0 > ω-B97x-D ~ B3P86 ~ B3LYP ~ CAM-B3LYP > TPSSh > PBE ~ BLYP ~ BHandHLYP >> M06 >> M06-2X. Concerning the basis sets, the triple-ζ def2-TZVP performs better than the double-ζ LANL2DZ. With the functional HSE06 and the basis set def2-TZVP the MAPD with respect to the experimental λmax values is 1.59% with a standard deviation of 1.17%. The absorption electronic spectra were interpreted in terms of vertical excitations between occupied and virtual MOs based on Ni-d atomic orbitals. The electronic structure of the Ni(II) species was finally calculated and discussed.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.