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  • Correspondence
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Reply to 'Dark channel fluorescence...' and 'Dips and peaks...'

Nature Chemistry volume 4, pages 767–768 (2012)Cite this article

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Aziz et al . reply to Regier et al . and de Groot — Dips appearing in the total fluorescence yield (TFY) at the L-edge spectra of 3d-transition metal ions in aqueous solution were recently argued to be useful for characterizing ultrafast charge-transfer processes to the solvent1,2. Yet, to prove experimentally such charge delocalization, additional studies would be required that are capable of explicitly tracking electronic relaxation channels. Indeed, the existence of the charge-delocalization channel (leading to a quenched fluorescence) has been, in our opinion, unequivocally demonstrated in a later comparative study of the transmission, TFY and the partial electron yield X-ray absorption measurement of aqueous Co2+ (ref. 3). Here the key is that the resonant photoelectron spectra do provide detailed insight into the actual electronic transients and the respective energies, involved in the electronic decay3.

As was pointed out by Regier et al.4 and de Groot5, the analysis of TFY spectra from transition-metal aqueous solution is complicated owing to competing signal contributions from solute and solvent, causing sub-background intensity. This view is particularly emphasized by Regier et al., who present results for the solid-state analogue and whose arguments we feel are very qualitative. The authors apply the inverse partial fluorescence yield (iPFY) method, which they correctly claim to be a bulk sensitive method, delivering an X-ray absorption spectrum, free from artefacts such as saturation. We have recently used this method in conjunction with the liquid micro-jet technique and indeed confirm the bulk-sensitivity aspect. However, the sole use of iPFY does not allow a conclusive explanation of the existence of the charge-delocalization channel6.

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Change history

  • 29 June 2017

    The Article 'Charge transfer to solvent identified using dark channel fluorescence-yield L-edge spectroscopy' by E. F. Aziz et al. (Nature Chemistry 2, 853–857; 2010) on which this Correspondence is based was retracted by the authors on 29 June 2017.

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Authors and Affiliations

  1. Helmholtz-Zentrum Berlin für Materialien und Energie, c/o BESSY GmbH, Albert-Einstein-Strasse 15, Berlin, 12489, Germany

    Emad F. Aziz

  2. Department of Physics, Freie Universität Berlin, Arnimallee 14, Berlin, 14195

    Emad F. Aziz

  3. Max-Born Institut Berlin, Max-Born-Str. 2a, Berlin, 12489

    Kathrin M. Lange

  4. Institut des Sciences Moléculaires, UMR 5255 CNRS, Université Bordeaux 1, 351 cours de la Libération, Talence Cedex, 33405, France

    Sébastien Bonhommeau

  5. Ecole Polytechnique Fédérale de Lausanne, Laboratoire de Spectroscopie Ultrarapide, Faculté des Sciences de Base, ISIC, Station 6, Lausanne, CH-1015, Switzerland

    Majed Chergui

Authors
  1. Emad F. Aziz
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  2. Kathrin M. Lange
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  3. Sébastien Bonhommeau
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  4. Majed Chergui
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Correspondence to Emad F. Aziz or Majed Chergui.

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Aziz, E., Lange, K., Bonhommeau, S. et al. Reply to 'Dark channel fluorescence...' and 'Dips and peaks...'. Nature Chem 4, 767–768 (2012). https://doi.org/10.1038/nchem.1449

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