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"The ketene intermediate in the photochemistry of ortho-nitrobenzaldehyde
" S. Laimgruber, T. Schmierer, P. Gilch, K. Kiewisch, J. NeugebauerPhys. Chem. Chem. Phys. 10 (2008) 3872-3882 Abstract: The first intermediate of the photochemical transformation of ortho-nitrobenzaldehyde to ortho-nitrosobenzoic acid in acetonitrile solvent has been characterized by femtosecond spectroscopy and time-dependent density functional theory (TDDFT) calculations. Femtosecond stimulated Raman spectroscopy (FSRS) indicates that this intermediate adopts a ketene structure. This assignment is supported by the TDDFT results. A kinetic analysis of FSRS and transient absorption data points to two channels for the formation of the ketene. For the predominating first channel the formation takes 0.4 ps. For the second channel it is much slower and takes 220 ps. We assign the first channel to a reaction via an excited singlet state. The second one might involve a triplet state. BMO authors (in alphabetic order): Peter Gilch Stefan Laimgruber Thomas Schmierer  WWW-Version |
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Letzte Änderung: 2016-09-14 13:34
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