Accurate prediction of vertical electronic transitions of Ni(II) coordination compounds via time dependent density functional theory
Sciortino, Giuseppe (Universitat Autònoma de Barcelona. Departament de Química)
Lihi, Norbert (University of Debrecen)
Czine, Tamás (University of Debrecen. Department of Inorganic and Analytical Chemistry)
Maréchal, Jean-Didier (Universitat Autònoma de Barcelona. Departament de Química)
Lledós, Agustí (Universitat Autònoma de Barcelona. Departament de Química)
Garribba, Eugenio (Università di Sassari. Dipartimento di Chimica e Farmacia)

Data:	2018
Resum:	Time dependent density functional theory calculations are completed for five Ni(II) complexes formed by polydentate peptides to predict the electronic absorption spectrum. The ligands examined were glycyl-glycyl-glycine (GGG), glycyl-glycyl-glycyl-glycine (GGGG), glycyl-glycyl-histidine (GGH), glycyl-glycyl-cysteine (GGC), and triethylenetetramine (trien). Fifteen functionals and two basis sets were tested. On the basis of the mean absolute percent deviation (MAPD), the ranking among the functionals is: HSE06 ∼ MPW1PW91 ∼ PBE0 > ω-B97x-D ∼ B3P86 ∼ B3LYP ∼ CAM-B3LYP > PBE ∼ BLYP ∼ BP86 > TPSS > TPSSh > 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 basis set def2-TZVP the MAPD with respect to the experimental λmax is 1. 65% with a standard deviation of 1. 26%. 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 is also discussed.
Ajuts:	Ministerio de Economía y Competitividad CTQ2014-54071-P
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Llengua:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Matèria:	UV-Vis spectroscopy ; Electronic structure ; Nickel ; Peptides ; Time dependent density functional theory
Publicat a:	International Journal of Quantum Chemistry, Vol. 118, Issue 16 (August 2018) , p. e25655, ISSN 1097-461X

DOI: 10.1002/qua.25655

Postprint 24 p, 1.7 MB

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