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Theoretical and experimental study of the Norrish I photodissociation of aromatic ketones

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Abstract

A set of selected acetophenone derivatives was investigated using absorption and emission spectroscopy, laser flash photolysis and DFT calculations. The triplet state lifetimes and the activation energy of the cleavage reaction were measured. Computed triplet-triplet absorption spectra were found in very good agreement with the experimental ones. Bond dissociation energies, activation energies, partial charges, ground state geometries were calculated. The transition state theory TST was successfully used to calculate the cleavage rate constants: a very good correlation was found between the experimental and the calculated values. It is found that the entropy change influences the preexponential factor. This study also points out the role of the partial charges in the transition state, although this effect alone does not account for the reaction rate constants.

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Authors and Affiliations

  1. Department of Photochemistry, UMR 7525 CNRS, University of Haute Alsace, ENSCMu, 3 rue Alfred Werner, 68093, Mulhouse Cedex, France

    Céline Dietlin, Xavier Allonas & Jean-Pierre Fouassier

  2. Laboratory of Organic and Bioorganic Chemistry, UMR 7015 CNRS, University of Haute Alsace, ENSCMu, 3 rue Alfred Werner, 68093, Mulhouse Cedex, France

    Albert Defoin

Authors
  1. Céline Dietlin
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  2. Xavier Allonas
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  3. Albert Defoin
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  4. Jean-Pierre Fouassier
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Correspondence to Xavier Allonas.

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This paper was published as part of the themed issue in honour of Jakob Wirz.

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Dietlin, C., Allonas, X., Defoin, A. et al. Theoretical and experimental study of the Norrish I photodissociation of aromatic ketones. Photochem Photobiol Sci 7, 558–565 (2008). https://doi.org/10.1039/b800546j

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