Charge transfer to solvent identified using dark channel fluorescence-yield L-edge spectroscopy
Authors: Emad F Aziz
Kathrin M Lange
Majed Chergui
M Hannelore Rittmann-Frank
Sébastien Bonhommeau
Journal: Nature Chemistry (2010)
Discipline: CHEMISTRY
Keywords: Aqueous ions; solute-solvent interactions; transition-metal ions; soft X-ray L-edge spectroscopy; d orbitals
Affiliations: Helmholtz-Zentrum Berlin für Materialien und Energie, c/o BESSY GmbH, Albert-Einstein-Strasse 15, 12489 Berlin, Germany. 

Abstract:  Aqueous ions are central to catalysis and biological function and play an important role in radiation biology as sources of damage-inducing electrons. Detailed knowledge of solute-solvent interactions is therefore crucial. For transition-metal ions, soft X-ray L-edge spectroscopy allows access to d orbitals, which are involved in chemical bonding. Using this technique, we show that the fluorescence-yield spectra of aqueous ionic species exhibit additional features compared with those of non-aqueous solvents. Some features dip below the fluorescence background of the solvent and this is rationalized by the competition between the fluorescence yields of the solute and solvent species, and between the solute radiative (fluorescence) and non-radiative channels; in particular, electron transfer to the water molecules. This method allows us to determine the nature, directionality and timescale of the electron transfer. Remarkably, we observe such features even for fully ligated metal atoms, which indicates a direct interaction with the water molecules. 

Retracted: Yes

PubPeer comments:
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  We could not identify the origin of the problem and we believe it might have arisen from an incorrect processing of the original data files. (Source: Erratum to the article: u201cCharge transfer to solvent identified using dark channel fluorescence-yield L-edge spectroscopyu201d, NATURE CHEMISTRY 2 (2010) 853) You have really no clue? , 
 It is a shame. Especially the argue against data invention in a spectral region of minor interest (u2018u2026that the area from 730 till 735 has no meaning information and not relevant to the article topicu2026u2019 their own words) unmasks one of the authors as primitive forger i.e. a vindication is not possible. The arguer is not worth to be member of the scientific community and must lose all academic degrees as has happened in the case of Jan Hendrik Schon. I wonder that the German Scientific Community is obviously not able to clean up. They should learn how to treat such cases from the Bell Laboratories. And once again a so-called high ranked journal (nature chemistry) turned out to be inferior (yellow press). , 
 Oh the retraction just went online on Nat. Chem. It would interesting if the authors ( unregistered sumbimission ) try to clarify his her point from some months ago:  the original data has been sent to the editor . Such a shame... , 
 Another paper seems to be affected (Aziz et al., Phys. Rev. Lett. 102, 068103 (2009)):  In view of the recent withdrawal of a paper in Nature Chemistry [1], we reinvestigated the Hemin data published in our Letter in Physical Review Letters as it seems that the same data have been used in both publications. Unfortunately, we found some inconsistencies between the published trace [Fig. 1(b)] in our Letter and some of the traces found in unpublished drafts of the Letter as well as the trace published in Nature Chemistry. This refers to some details of the reported line shape as well as the concentration value of the sample given in either paper (1 mM vs 3 mM). The original data is no longer available and therefore we have decided to ask for a withdrawal of this data published in the Letter. , 
 #1 The same is also true for [Fe(bpy)3]2+ in acetonitrile (Fig. 2c), where to trace has also been elongated by appending it with small duplicated fragments at around 730 and 733 eV. In the light that the area between 730 and 735 eV has no meaning, I am particularly puzzled why this has been done?!? , 
 This paper was retracted in 2017, but it might be worth posting an illustration of the problems that were first noticed by Unreg in comment #1. ![file] This retraction was also featured at Retraction Watch, see here: https: retractionwatch.com 2017 07 13 nature-chemistry-issues-first-retraction ,