We present a study of charge transfer in Na-intercalated FeOCl and polyaniline-intercalated FeOCl using high-resolution x-ray absorption spectroscopy and resonant x-ray emission spectroscopy at the FeK edge. By comparing the experimental data with ab initio simulations, we are able to unambiguously distinguish the spectral changes which appear due to intercalation into those of electronic origin and those of structural origin. For both systems, we find that about 25% of the Fe sites are reduced to Fe2⊃+ via charge transfer between FeOCl and the intercalate. This is about twice as large as the Fe2⊃+ fraction reported in studies using Mössbauer spectroscopy. This discrepancy is ascribed to the fact that the charge transfer occurs on the same time scale as the Mössbauer effect itself. Our result suggests that every intercalated atom or molecule is involved in the charge-transfer process, thus making this process a prerequisite for intercalation. The Fe2⊃+ fraction is found to increase with pressure for polyaniline-FeOCl, hinting at an enhancement of the conductivity in the FeOCl intercalation compounds under pressure.
|Journal||Physical Review B - Condensed Matter and Materials Physics|
|State||Published - 26 Oct 2010|