Crystal structure of impurity-free rhodochrosite (MnCO3) and thermal expansion properties

  • Wen LiangEmail author
  • Lin Li
  • Rui Li
  • Yuan Yin
  • Zeming Li
  • Xiqiang Liu
  • Shuangmin Shan
  • Yu He
  • Yong Meng
  • Zengsheng Li
  • Heping LiEmail author
Original Paper


To explain the anomalous anisotropy in thermal expansion properties reported in rhodochrosite (MnCO3) previously Rao and Murthy (J Mater Sci 5: 82, 1970), Li et al. (High Temp High Press, 2019), the evaluation of crystal structure is thought to be indispensable as an important aspect in mineralogy. In this spirit, single crystals of impurity-free rhodochrosite, up to 100 μm in size, were synthesized under high-pressure–temperature (PT) conditions. The standard crystal structure, without the impurities common to natural samples, was investigated by means of single-crystal X-ray diffraction (XRD). The unit cell parameters obtained for the \(R\overline{3}c\) symmetry were a = 4.7754(5) Å and c = 15.6484(18) Å, with a final R value of 0.0162. The (MnO6) octahedron exhibits an anomalous bond angle that tends more toward 90° of a regular octahedron, which is totally different from those of MgCO3, FeCO3, and CaCO3. Using the single-crystal XRD from 100 to 370 K, the thermal expansion coefficients were quantified as αa = 5.08 × 10−6 K−1 and αc = 18.06 × 10–6 K−1, as well as αVunit cell = 28.49 × 10–6 K−1. The geometry of (MnO6) octahedron as function of temperature was also determined as αMn–O = 12.14 × 10−6 K−1 and αO–Mn–O ≈ 0.05°/100 K. The anisotropy of MnCO3 (αa/αc = 3.55), similar to that of MgCO3 (~ 3.0, Markgraf and Reeder, Am Mineral, 70: 590–600, 1985), indicates that the difference in bond angle has no significant effect on the thermal expansion properties. According to the standard crystal structures of end members (MgCO3, FeCO3, MnCO3, and CaCO3), the cation substitution in calcite-type structures is proven to agree with the rigid body model and the linear solid solution relationship is highly consistent with those of natural carbonates.


Impurity-free rhodochrosite single crystal Crystal structure Single-crystal XRD Thermal expansion 



We appreciate two anonymous reviewers for their valuable comments and suggestions. We acknowledge Jung-Fu Lin from University of Texas at Austin for constructive discussion in carbonate minerals. This work was financially supported by Major State Research Development Program of China (2016YFC0601101), the National Science Foundation for Young Scientists of China (41802044), National Natural Fund of China (4160030283), the Strategic Priority Research Program (B) of Chinese Academy of Sciences (XDB 18010401), 135 Program of the Institute of Geochemistry (Y2ZZ041000), CAS, and the Western Light (Y8CR028).

Supplementary material

269_2019_1078_MOESM1_ESM.doc (291 kb)
Supplementary file1 (DOC 291 kb)


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2020

Authors and Affiliations

  • Wen Liang
    • 1
    Email author
  • Lin Li
    • 2
    • 6
  • Rui Li
    • 1
    • 3
  • Yuan Yin
    • 1
    • 3
  • Zeming Li
    • 1
    • 3
  • Xiqiang Liu
    • 1
    • 3
  • Shuangmin Shan
    • 1
  • Yu He
    • 1
  • Yong Meng
    • 4
  • Zengsheng Li
    • 5
  • Heping Li
    • 1
    Email author
  1. 1.Key Laboratory of High Temperature and High Pressure Study of the Earth’s Interior, Institute of GeochemistryChinese Academy of SciencesGuiyangChina
  2. 2.State Key Laboratory of Geological Processes and Mineral ResourcesChina University of GeosciencesBeijingChina
  3. 3.University of Chinese Academy of SciencesBeijingChina
  4. 4.State Key Laboratory of Ore Deposit Geochemistry, Institute of GeochemistryChinese Academy of SciencesGuiyangChina
  5. 5.Shandong Geological Sciences InstituteJinanChina
  6. 6.Institute of Science ResearchChina University of GeosciencesBeijingChina

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