Accurate prediction of vertical electronic transitions of Ni(II) coordination compounds via time dependent density functional theory

Sciortino, Giuseppe and Lihi, Norbert and Czine, Tamás and Marechal, Jean-Didier and Lledós, Agustí (2018) Accurate prediction of vertical electronic transitions of Ni(II) coordination compounds via time dependent density functional theory. INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 118 (16). pp. 1-23. ISSN 0020-7608

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Abstract

Time dependent d. functional theory calcns. are completed for five Ni(II) complexes formed by polydentate peptides to predict the electronic absorption spectrum. The ligands examd. 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 abs. 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 exptl. λmax is 1.65% with a std. deviation of 1.26%. The absorption electronic spectra were interpreted in terms of vertical excitations between occupied and virtual MOs based on Ni-d AOs. The electronic structure of the Ni(II) species is also discussed. [on SciFinder(R)]

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