Electronic states of RFe2O4(R=Lu,Yb,Tm,Y) mixed-valence compounds determined by soft x-ray absorption spectroscopy and x-ray magnetic circular dichroism

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We here report an investigation of the electronic states in the RFe2O4(R=Lu,Yb,Tm,Y) mixed-valence ferrites by means of soft x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) measurements together with ab initio theoretical calculations. The presence of Fe+2 and Fe+3 pure ionic species is discarded in the XAS spectra at the OK edge in both experimental data and simulations based on the multiple scattering theory. Similarly, no trace of Fe+2/Fe+3 contributions is detected in the XMCD spectra at the FeK edge. On the other hand, the XAS and XMCD spectra at the FeL2,3 edges can be well described in terms of Fe+2/Fe+3 contributions, and are also supported by multiplet calculations. This finding can be interpreted as the existence of a mixture of 3d5/3d6 configurations at the Fe atoms. Alternative ferrimagnetic spin orderings based on a trimodal Fe valence distribution are also proposed and discussed. Finally, a possible explanation for the strong dependence of the FeL2,3 edges XMCD signal magnitude on both the sample surface preparation and detection method is presented.
Financial support from the Spanish MINECO (Project No. MAT2012-38213-C02-01) and Diputación General de Aragón (DGA-CAMRADS) is acknowledged.