title: Electronic excitations in Fischer-type Cr and W aminocarbene complexes: a combined ab initio and experimental study.
abstract: The influence of the substitution on the carbene ligand in the series of Fischer-type Cr and W aminocarbene complexes was studied experimentally by UV-vis spectroscopy and theoretically by comparative ab initio SA-CASSCF/MS-CASPT2 and TD-DFT methods. Both calculations interpreted the experimental UV-vis spectra and their variations caused by substitution effects well. TD-DFT analysis of individual transitions using electron density redistributions indicated that the variation of the absorption spectra due to substitution is accompanied by a change in the character of the low-lying excited states participating in the visible bands. Correlated MS-CASPT2 calculations confirmed the TD-DFT assignments of the lowest-lying transitions in the visible region almost quantitatively.
authors.affiliation: J. Heyrovský Institute of Physical Chemistry, v.v.i., Academy of Sciences of the Czech Republic , Dolejškova 3, 182 23 Prague 8, Czech Republic.
authors.forename: Hana
authors.initials: H
authors.lastname: Kvapilová
authors.forename: Irena
authors.initials: I
authors.lastname: Hoskovcová
authors.forename: Megumi
authors.initials: M
authors.lastname: Kayanuma
authors.forename: Chantal
authors.initials: C
authors.lastname: Daniel
authors.forename: Stanislav
authors.initials: S
authors.lastname: Záliš