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Title

Application of Transient Grating Spectroscopy to the Study of the Energetic and Dynamics of Electron Transfer Reactions: Separation of an Ion Pair into Free Ions

Authors
Henseler, Arthur
Published in Journal of Photochemistry and Photobiology. A, Chemistry. 1998, vol. 112, no. 2-3, p. 103-109
Abstract The enthalpy of formation of the free ions generated by the electron transfer between benzophenone in the lower triplet state and 1,4-diazabicyclo[2,2,2]octane in acetonitrile has been measured using transient thermal phase grating. This enthalpy is smaller by more than 0.14±0.08 eV than the enthalpy of formation of the geminate ion pair obtained from a previous ps thermal phase grating investigation. Therefore, the dissociation of a geminate ion pair into free ions in endothermic. However, separation is exergonic if translational entropy in taken into account. A small and positive value of C, the correction term in the Rehm—Weller equation, is obtained if this term is considered as a free energy. The principles of the transient grating technique as a tool for investigating photoinduced processes in solution are briefly reviewed.
Keywords Free ionsEnthalpyTransient grating technique
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Research group Groupe Vauthey
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VAUTHEY, Eric, HENSELER, Arthur. Application of Transient Grating Spectroscopy to the Study of the Energetic and Dynamics of Electron Transfer Reactions: Separation of an Ion Pair into Free Ions. In: Journal of Photochemistry and Photobiology. A, Chemistry, 1998, vol. 112, n° 2-3, p. 103-109. https://archive-ouverte.unige.ch/unige:2944

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Deposited on : 2009-09-21

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