NdBaFe2O5+w and steric effect of Nd on valence mixing and ordering of Fe

J. Lindén, P. Karen*

*Corresponding author for this work

    Research output: Contribution to journalArticleScientificpeer-review

    9 Citations (Scopus)


    NdBaFe2O5 above and below Verwey transition is studied by synchrotron X-ray powder diffraction and Mssbauer spectroscopy and compared with GdBaFe2O5 that adopts a higher-symmetry charge-ordered structure typical of the SmHo variants of the title phase. Differences are investigated by Mssbauer spectroscopy accounting for iron valence states at their local magnetic and ionic environments. In the charge-ordered state, the orientation of the electric-field gradient (EFG) versus the internal magnetic field (B) agrees with experiment only when contribution from charges of the ordered dxz orbitals of Fe 2 is included, proving thus the orbital ordering. The EFG magnitude indicates that only some 60% of the orbital order occurring in the SmHo variants is achieved in NdBaFe2O5. The consequent diminishing of the orbit contribution (of opposite sign) to the field B at the Fe2 nucleus explains why B is larger than for the SmHo variants. The decreased orbital ordering in NdBaFe2O5 causes a corresponding decrease in charge ordering, which is achieved by decreasing both the amount of the charge-ordered iron states in the sample and their fractional valence separation as seen by the Mssbauer isomer shift. The charge ordering in NdBaFe2O5w is more easily suppressed by the oxygen nonstoichiometry (w) than in the SmHo variants. Also the valence mixing into Fe2.5 is destabilized by the large size of Nd. The orientation of the EFG around this valence-mixed iron can only be accounted for when the valence-mixing electron is included in the electrostatic ligand field. This proves that the valence mixing occurs between the two iron atoms facing each other across the structural plane of the rare-earth atoms.

    Original languageEnglish
    Pages (from-to)2703-2713
    Number of pages11
    JournalJournal of Solid State Chemistry
    Issue number11
    Publication statusPublished - Nov 2010
    MoE publication typeA1 Journal article-refereed


    • Charge ordering
    • Electric-field gradient
    • Mixed valence
    • Mssbauer spectroscopy
    • Orbital ordering
    • Quadrupole coupling constant
    • Valence mixing


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