Impact of vibrational excitation on the kinetics of a nascent ketene

Phys Chem Chem Phys. 2009 Dec 28;11(48):11596-607. doi: 10.1039/b915451e. Epub 2009 Nov 5.

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 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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Benzaldehydes / chemistry*
  • Ethylenes / chemistry*
  • Ketones / chemistry*
  • Kinetics
  • Photochemistry
  • Spectrophotometry, Infrared
  • Spectrophotometry, Ultraviolet

Substances

  • Benzaldehydes
  • Ethylenes
  • Ketones
  • 2-nitrobenzaldehyde
  • ketene