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"Impact of Vibrational Excitation on the Kinetics of a Nascent Ketene" Thomas Schmierer, Wolfgang J. Schreier, Florian O. Koller, Tobias E. Schrader, Peter GilchPhys. Chem. Chem. Phys. 11 (2009) 11596 Abstract: The formation and decay of a ketene intermediate photochemically formed from o-nitrobenzaldehyde has been studied by femtosecond UV/Vis and IR spectroscopy. The ketene is formed predominantly within a few 100 fs and to a minor extent within 200 ps via the recombination of a triplet phased bi-radical. In tetrahydrofuran solution the ketene intermediate is seen to form a secondary intermediate with biphasic kinetics. The first phase of this decay occurs within a few picoseconds. It can be attributed to the reaction of vibrationally excited ketenes. The second phase characterized by a time constant of 2 ns is due to the reaction of thermalized molecules. In 2-butanol solution the lifetime of the thermalized ketene is only 60 ps and the rapid and the slow phases of the decay start to merge. BMO authors (in alphabetic order): Peter Gilch Florian Koller Thomas Schmierer Tobias Schrader Wolfgang Schreier Assoziierte Projekte: The flow of vibrational energy in molecules Femtosecond Stimulated Raman Spectroscopy in the "Blue" Mechanisms of Complex Photoreactions  WWW-Version |