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Dark channel fluorescence observations result from concentration effects rather than solvent–solute charge transfer

Nature Chemistry volume 4, pages 765–766 (2012)Cite this article

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To the Editor

In the October 2010 issue of Nature Chemistry, Aziz, Chergui and co-authors reported on the supposed observation of solute–solvent charge transfer using a method called 'dark-channel' fluorescence yield spectroscopy1. This method was subsequently discussed by Nilsson in a News and Views article2. Aziz, Chergui and collaborators explain that coordination between aqueous Fe ions and water can result in a decrease in the radiative decay rates of the Fe 2p core hole due to charge transfer. They propose that concentration-dependent changes to the Fe fluorescence efficiency alter a sub-background or negative edge feature that is observed in the total fluorescence detected X-ray absorption spectrum, commonly referred to as the total fluorescence yield (TFY). Concentration-dependent measurements of aqueous FeCl3 showing changing sub-background regions, and a measurement of FeCl3 dissolved in ethanol, showing no sub-background region, are provided to support their conclusions. They claim that their observations are due to charge transfer, but it is our view that the changes in the intensity of the sub-background and its structure can be attributed to changes in the magnitudes of the Fe and O partial fluorescence yields (PFY) resulting from modification of the Fe:O ratio in their samples.

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Figure 1: The excitation–emission matrix, extracted partial fluorescence yields and total electron yield of solid α-Fe2O3.

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 (Nature Chemistry 2, 853–857; 2010) on which this Correspondence is based was retracted by the authors on 29 June 2017.

References

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Acknowledgements

This research is supported by NSERC. The research described in this Correspondence was performed at the Canadian Light Source, which is supported by NSERC, NRC, CIHR and the University of Saskatchewan.

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Authors and Affiliations

  1. Canadian Light Source, University of Saskatchewan, 101 Perimeter Road, Saskatoon, S7N 0X4, Canada

    T. Z. Regier

  2. Department of Physics and Engineering Physics, University of Saskatchewan, 116 Science Place, Saskatoon, S7N 5E2, Canada

    T. Z. Regier & J. S. Tse

  3. Department of Physics and Astronomy, University of Waterloo, 200 University Ave. West, Waterloo, N2L 3G1, Canada

    A. J. Achkar & D. G. Hawthorn

  4. College of Agriculture and Bioresources, University of Saskatchewan, 51 Campus Drive, Saskatoon, S7N 5A8, Canada

    D. Peak

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  1. T. Z. Regier
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  2. A. J. Achkar
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  3. D. Peak
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  4. J. S. Tse
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  5. D. G. Hawthorn
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Contributions

T.Z.R. wrote the correspondence and performed the data analysis. D.P. performed the measurement. All authors contributed to the development of the concepts.

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Correspondence to T. Z. Regier.

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Regier, T., Achkar, A., Peak, D. et al. Dark channel fluorescence observations result from concentration effects rather than solvent–solute charge transfer. Nature Chem 4, 765–766 (2012). https://doi.org/10.1038/nchem.1430

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