Elsevier

Chemical Physics Letters

Volume 162, Issues 4–5, 20 October 1989, Pages 269-276
Chemical Physics Letters

Investigation of UV laser-induced unimolecular isomerization of azulene to naphthalene in a collision-free molecular beam

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Abstract

The unimolecular isomerization of vibrationally excited (λ=351 nm) azulene (C10H8) to naphthalene is observed in a fully expanded (collision-free) continuous molecular beam. A shift between the ionization curves of the parent peaks of the two isomers as a function of electron impact energy is measured with a mass spectrometer and used to detect isomerization. With a measurement of the degree of excitation with a bolometer, the isomerization rate constant has been determined to be 600±310 s−1 at a total internal energy of about 4.1 eV. This rate constant is compared with that estimated from previous shock-wave experiments analyzed by means of RRKM theory. At nozzle temperatures higher than 600 K, isomerization of non-laser excited azulene is observed and attributed to wall collisions in the hot beam source.

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    Present address: Stanford University, Department of Chemistry, Stanford, CA 94305-5080, USA.

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