title: UV-visible absorption spectra of [Ru(E)(E')(CO)(2)(iPr-DAB)] (E = E' = SnPh(3) or Cl; E = SnPh(3) or Cl, E' = CH(3); iPr-DAB = N,N'-Di-isopropyl-1,4-diaza-1,3-butadiene): combination of CASSCF/CASPT2 and TD-DFT calculations.
abstract: The UV-visible absorption spectra of [Ru(E)(E')(CO)(2)(iPr-DAB)] (E = E' = SnPh(3) or Cl; E = SnPh(3) or Cl, E' = CH(3); iPr-DAB = N,N'-di-isopropyl-1,4-diaza-1,3-butadiene) are investigated using CASSCF/CASPT2 and TD-DFT calculations on model complexes [Ru(E)(E')(CO)(2)(Me-DAB)] (E = E' = SnH(3) or Cl; E = SnH(3) or Cl, E' = CH(3); Me-DAB = N,N'-dimethyl-1,4-diaza-1,3-butadiene). The calculated transition energies and oscillator strengths allow an unambiguous assignment of the spectra of the nonhalide complexes [Ru(SnPh(3))(2)(CO)(2)(iPr-DAB)] and [Ru(SnPh(3))(Me)(CO)(2)(iPr-DAB)]. The agreement between the CASSCF/CASPT2 and TD-DFT approaches is remarkably good in the case of these nonhalide complexes. The lowest-energy part of the spectrum (visible absorption) originates in electronic transitions that correspond to excitations from the axial E-Ru-E' sigma(2) orbital into the low-lying pi(DAB) orbital (sigma-bond-to-ligand charge transfer, SBLCT, transitions), while the absorption between 25 000 and 35 000 cm(-1) is due to metal-to-ligand charge transfer (MLCT) excitations from the 4d(Ru) orbitals to pi(DAB) (MLCT). Above 35 000 cm(-1), the transitions mostly correspond to MLCT and SBLCT excitations into pi(CO) orbitals. Analysis of the occupied sigma orbitals involved in electronic transitions of the nonhalide complexes shows that the Kohn-Sham orbitals are generally more delocalized than their CASSCF/CASPT2 counterparts. The CASSCF/CASPT2 and TD-DFT approaches lead to different descriptions of electronic transitions of the halide complexes [Ru(Cl)(2)(CO)(2)(Me-DAB)] and [Ru(Cl)(Me)(CO)(2)(Me-DAB)]. CASSCF/CASPT2 reproduces well the observed blue-shift of the lowest absorption band on going from the nonhalide to halide complexes. TD-DFT systematically underestimates the transition energies of these complexes, although it reproduces the general spectral features. The CASSCF/CASPT2 and TD-DFT techniques differ significantly in their assessment of the chloride contribution. Thus, CASSCF/CASPT2 assigns the lowest-energy absorption to predominantly Ru --> DAB MLCT transitions, while TD-DFT predicts a mixed XLCT/MLCT character, with the XLCT component being predominant. (XLCT stands for halide (X)-to-ligand-charge transfer.) Analysis of Kohn-Sham orbitals shows a very important 3p(Cl) admixture into the high-lying occupied orbitals, in contrast to the CASSCF/CASSPT2 molecular orbitals which are nearly pure 4d(Ru) with the usual contribution of the back-donation to pi(CO) orbitals. Further dramatic differences were found between characters of the occupied sigma orbitals, as calculated by CASSCF/CASPT2 and DFT. They differ even in their bonding character with respect to the axial E-Ru and Cl-Ru bonds. These differences are attributed to a drawback of the DFT technique with respect to the dynamical correlation effects which become very important in complexes with a polar Ru-Cl bond. Similar differences in the CASSCF/CASPT2 and TD-DFT descriptions of the lowest allowed transition of [Ru(Cl)(2)(CO)(2)(Me-DAB)] and [Ru(Cl)(Me)(CO)(2)(Me-DAB)] were found by comparing the changes of Mulliken population upon excitation. This comparison also reveals that CASSCF/CASPT2 generally predicts smaller electron density redistribution upon excitation than TD-DFT, despite the more localized character of CASSCF/CASPT2 molecular orbitals.
authors.affiliation: Laboratoire de Chimie Quantique UMR 7551 CNRS / Université Louis Pasteur Institut LeBel, 4 Rue Blaise Pascal, F- 67 000 Strasbourg, France.
authors.forename: M
authors.initials: M
authors.lastname: Turki
authors.forename: C
authors.initials: C
authors.lastname: Daniel
authors.forename: S
authors.initials: S
authors.lastname: Zális
authors.forename: A
authors.initials: A
authors.lastname: Vlcek
authors.forename: J
authors.initials: J
authors.lastname: van Slageren
authors.forename: D J
authors.initials: DJ
authors.lastname: Stufkens