Impact of vibrational excitation on the kinetics of a nascent ketene

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 approximately 200 ps via the recombination of a triplet pha...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2009-01, Vol.11 (48), p.11596-11607
Main Authors: SCHMIERER, Thomas, SCHREIER, Wolfgang J, KOLLER, Florian O, SCHRADER, Tobias E, GILCH, Peter
Format: Article
Language:English
Subjects:
Benzaldehydes - chemistry
Chemistry
Ethylenes - chemistry
Exact sciences and technology
General and physical chemistry
Ketones - chemistry
Kinetics
Photochemistry
Spectrophotometry, Infrared
Spectrophotometry, Ultraviolet
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Summary: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 approximately 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 approximately 60 ps and the rapid and the slow phases of the decay start to merge.
ISSN:1463-9076
1463-9084
DOI:10.1039/b915451e