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

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• 作者：Hana Kvapilov谩 ; Irena Hoskovcov谩 ; Megumi Kayanuma ; Chantal Daniel ; Stanislav Z谩li拧
• 刊名：Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：November 14, 2013
• 年：2013
• 卷：117
• 期：45
• 页码：11456-11463
• 全文大小：422K
• 年卷期：v.117,no.45(November 14, 2013)
• ISSN：1520-5215

文摘

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鈥搗is spectroscopy and theoretically by comparative ab initio SA-CASSCF/MS-CASPT2 and TD-DFT methods. Both calculations interpreted the experimental UV鈥搗is 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.