Electronic structures and photoelectron spectra of zinc(II) bis-β-diketonates

Application of DFT for the modeling of the valence region photoelectron spectra of boron and d‐element complexes and macromolecules

“…For DFT calculations, we used the Firefly 7.1.G and GAMESS program packages, with the B3LYP5 hybrid exchange‐correlation functional and the TZVPP basis set unless otherwise specified. We selected this basis set based on test calculations and the successful use of theoretical models for electronic spectra interpretation . We calculated the Hessian to check the correspondence between the optimized structures and local minima of the potential energy surface.…”

Electronic structure and photoelectron spectra of nickel (II) acetylacetonate and its thio- and amino-substituted analogues

“…As shown in Refs. [17,18,21,41], the band for the p 3 -electrons in the PE spectra of the metal acetylacetates with a metaleligand ionic bonding exhibited a half-height width of 0.5e0.6 eV. For the PE spectra of Ni(аcac) 2 and hetero-substituted IIeIV, removing an electron from the anti-bonding MO in all compounds (Fig.…”

“…Our investigations of b-diketonate complexes of boron difluoride [18e20], Zn(acac) 2 and their thio-substitutes [21] using UPS and density functional theory (DFT) exhibited good spectral regularities based on the sequence and nature of KohneSham molecular orbitals. The UPS spectral interpretation to approximate the extended Koopmans' theorem, IE i ¼ eε i þ d i, where d i is a correction factor depending on the electron level (Koopmans' defect), improves the correlation of the calculated IE i values to the experimental ionization energies.…”

Electronic structure of nitrogen-containing intracomplex nickel(II) compounds based on ultraviolet photoelectron spectra and density functional theory

“…The attribution of the calculated energies of Kohn-Sham orbitals to the experimentalvalues of the vertical ionization energies (IEs) was carried out in the approximation of extended Koopmans' theorem IE v (i) = -ε(i) + δ(i) [17,18], which makes it possible to obtain the correspondence of the calculated energies ε(i) to the experimental IEs with regard to the dependence of the Koopmans' defect δ(i) on the character of the electronic level [8,19,20]. For the determination of the metal effect on the ligand molecular orbitals the complexes with the frozen geometry and hydrogen atom substitution for nickel were calculated.…”