Electronic Excitations in Fischer-Type Cr and W Aminocarbene Complexes: A Combined ab Initio and Experimental Study

0399710 - ÚFCH JH 2014 RIV US eng J - Článek v odborném periodiku
Kvapilová, Hana - Hoskovcová, Irena - Kayanuma, M. - Daniel, CH. - Záliš, Stanislav
Electronic Excitations in Fischer-Type Cr and W Aminocarbene Complexes: A Combined ab Initio and Experimental Study.
Journal of Physical Chemistry A. Roč. 117, č. 45 (2013), s. 11456-11463. ISSN 1089-5639. E-ISSN 1520-5215
Grant CEP: GA MŠMT LD11086
Institucionální podpora: RVO:61388955
Klíčová slova: METAL CARBENE COMPLEXES * FLASH-PHOTOLYSIS * BASIS-SETS
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 2.775, rok: 2013

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.
Trvalý link: http://hdl.handle.net/11104/0226947