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Magnetic and nuclear structure and thermal expansion of orthorhombic and monoclinic polymorphs of CoGeO3 pyroxene

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Abstract

CoGeO3 was synthesized at 1,273 and 1,448 K using ceramic sintering techniques in the monoclinic and orthorhombic modification, respectively. The two compounds were analysed by magnetic susceptibility measurements and neutron diffraction in order to study magnetic ordering and spin structures at low temperature. The monoclinic form of CoGeO3 has C2/c symmetry and orders magnetically below 36 K with a small negative paramagnetic Curie temperature θ P = −4.6 (2) K. The magnetic structure can be described with k = (1, 0, 0) in the magnetic space group C2′/c′ having a ferromagnetic spin arrangement within the chains of M1 sites, but a dominating antiferromagnetic coupling between the chains. At the M1 sites the magnetic spins are aligned within the a–c plane forming an angle of 120° with the +a-axis and they are not parallel to the spins at M2. Here spins are also ferromagnetically coupled within, but antiferromagnetically coupled between the M1/M2 site bands. The orthorhombic phase of CoGeO3 displays Pbca symmetry and transforms to an antiferromagnetically ordered state [θ P = −18.6(2) K] below 33 K. The magnetic spin structure can be described with k = (0, 0, 0) in space group Pbca′ and it is similar to the one of the C2/c phase except that it is non-collinear in nature, i.e. there are components of the magnetic moment along all three crystallographic axes. Small magneto-elastic coupling is observed in the orthorhombic phase.

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Notes

  1. The neutron diffraction pattern of Wiedenmann et al. (1986) probably was taken with λ ≈ 1.24 Å instead of 2.48 Å given in the text. With the later wavelength the Bragg peaks displayed in the Figure at higher angles would not be accessible.

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Acknowledgments

This work was supported by the Fonds zur Förderung der wissenschaftlichen Forschung, FWF, Vienna, under grants number R33-N10 and P19762/N10. Neutron diffraction experiments have been supported by the European Commission under the 7th Framework Programme through the “Research Infrastructures” action of the “Capacities” Programme, Contract No: CP_CSA_Infra-2008-1.1.1 Number 226507-NIMI3. Fernando Cámara and Fabrizio Nestola are thanked for their careful and helpful reviews of the manuscript.

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Authors and Affiliations

  1. Division of Mineralogy, Department of Materials Engineering and Physics, University of Salzburg, Hellbrunnertstr. 34, 5020, Salzburg, Austria

    Günther Josef Redhammer, Gerold Tippelt & Georg Amthauer

  2. Institute for Materials Science, Darmstadt University of Technology, Petersenstrasse 23, 64287, Darmstadt, Germany

    Anatoliy Senyshyn

  3. Department of Chemistry, Philipps-University Marburg, Hans Meerweinstr., 35032, Marburg/Lahn, Germany

    Clemens Pietzonka

  4. Institute of Crystallography, RWTH Aachen University, Jägerstr. 17/19, 52056, Aachen, Germany

    Georg Roth

  5. Forschungsneutronenquelle Heinz Maier-Leibnitz FRM II, Lichtenbergstrasse 1, 85747, Garching, Germany

    Anatoliy Senyshyn

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  1. Günther Josef Redhammer
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Correspondence to Günther Josef Redhammer.

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Redhammer, G.J., Senyshyn, A., Tippelt, G. et al. Magnetic and nuclear structure and thermal expansion of orthorhombic and monoclinic polymorphs of CoGeO3 pyroxene. Phys Chem Minerals 37, 311–332 (2010). https://doi.org/10.1007/s00269-009-0335-x

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