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J Am Chem Soc. 2012 Sep 26;134(38):15953-62. Epub 2012 Sep 14.

Elucidating the mechanism of multiferroicity in (NH4)3Cr(O2)4 and its tailoring by alkali metal substitution.

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  • 1Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States.


The antiferromagnetic Cr(V) peroxychromates, M(3)Cr(O(2))(4), M = K, Rb, and Cs, become ferroelectric when mixed with NH(4)(+), but the underlying mechanism is not understood. Our dielectric relaxation, Raman scattering, and high-frequency EPR measurements on the M(3-x)(NH(4))(x)Cr(O(2))(4) family clarify this mechanism. At 295 K, (NH(4))(3)Cr(O(2))(4) is tetragonal (I42m), with the NH(4)(+) ions occupying two distinctly different sites, N1 and N2. A ferroelectric transition at T(c1) = 250 K is revealed by λ-type anomalies in C(p) and dielectric constant, and lowering of symmetry to Cmc2(1). Below T(c1), the N1 sites lose their tetrahedral symmetry and thus polarization develops. Raman detection of translational modes involving the NH(4)(+) ions around 193 cm(-1) supports this model. EPR around T(c1) revealed that the [Cr(O(2))(4)](3-) ions reorient by about 10°. A minor peak at T(c2) ≈ 207 K is attributed to a short-range ordering that culminates in a long-range, structural order at T(c3) ≈ 137 K. At T(c3), the symmetry is lowered to P1 with significant changes in the cell parameters. Rb(+) and Cs(+) substitutions that block the N1 and N2 sites selectively show that T(c1) is related to the torsional motion of the N1 site, while T(c2) and T(c3) are governed by the motional slowing down of the N2 site. These data show that the multiferroic behavior of this family is governed by the rotational and translational dynamics of the NH(4)(+) ions and is tunable by their controlled substitutions. Relevance to other classes of possible multiferroics is pointed out.

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