Interplay ofcomputational chemistry and transient absorption spectroscopy in the ultrafast studies
E.A. Pritchina1,2, N.P. Gritsan1,2, G.T. Burdzinski3,4, M.S. Platz4
1Institute of Chemical Kinetics and Combustion SB RAS, Novosibirsk, Russia
2Novosibirsk State University, Novosibirsk, Russia
3Quantum Electronics Laboratory, Faculty of Physics, Adam Mickiewicz University, Poznan, Poland
4Department of Chemistry, The Ohio State University, Columbus, Ohio, USA
Ключевые слова: femtosecond transient absorption spectroscopy, photochemical hydrogen transfer, photochemical acyl migration, electronic absorption spectra calculations, time-dependent density functional theory, CASSCF/CASPT2 procedure
Страницы: 63-70
Аннотация
The primary physical and chemical processes in the photochemistry of 1-(trideuteromethyl)-2,3,4-trideutero (1) and 1-acetoxy-2-methoxy- (2) 9,10-anthraquinones were studied using femtosecond transient absorption spectroscopy and computational chemistry. Excitation of 1 and 2 at 270 nm results in the population of a set of highly excited singlet states which decay within the laser pulse by internal conversion and vibrational energy redistribution. The transient absorption spectra of the lowest singlet and triplet excited states of substituted anthraquinones 1 and 2 as well as the triplet excited and ground states of the products were detected. The assignments of the transient absorption spectra were performed on the basis of quantum chemical calculations of the electronic absorption spectra of the intermediates. Time-dependent density functional theory or CASSCF/CASPT2 procedure were used to calculate the spectroscopic properties of the intermediates.
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