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Accurate prediction of vertical electronic transitions of Ni(II) coordination compounds via time dependent density functional theory
Author(s) -
Sciortino Giuseppe,
Lihi Norbert,
Czine Tamás,
Maréchal JeanDidier,
Lledós Agustí,
Garribba Eugenio
Publication year - 2018
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25655
Subject(s) - density functional theory , chemistry , basis set , atomic orbital , electronic structure , absorption spectroscopy , denticity , computational chemistry , crystallography , physics , quantum mechanics , crystal structure , electron
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 λ max 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.