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Issue 48, 2009

Impact of vibrational excitation on the kinetics of a nascent ketene

Author affiliations

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.

Graphical abstract: Impact of vibrational excitation on the kinetics of a nascent ketene

Article information


Submitted
29 Jul 2009
Accepted
28 Sep 2009
First published
05 Nov 2009

Phys. Chem. Chem. Phys., 2009,11, 11596-11607
Article type
Paper

Impact of vibrational excitation on the kinetics of a nascent ketene

T. Schmierer, W. J. Schreier, F. O. Koller, T. E. Schrader and P. Gilch, Phys. Chem. Chem. Phys., 2009, 11, 11596 DOI: 10.1039/B915451E

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