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    Quantum spin fluctuations and hydrogen bond network in the antiferromagnetic natural mineral henmilite

    Hajime Yamamoto1, Terutoshi Sakakura1, Harald O. Jeschke2, Noriyuki Kabeya3, Kanata Hayashi4, Yuya Ishikawa4, Yutaka Fujii4, Shunji Kishimoto5, Hajime Sagayama5 et al.

    Kei Shigematsu6,7, Masaki Azuma6,7, Akira Ochiai3, Yukio Noda1, and Hiroyuki Kimura1

    • 1Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira 2-1-1, Aoba, Sendai 980-8577, Japan
    • 2Research Institute for Interdisciplinary Science, Okayama University, Okayama 700-8530, Japan
    • 3Department of Physics, Tohoku University, Aoba 6-3, Aoba, Sendai 980-8577, Japan
    • 4Research Center for Development of Far-Infrared Region, University of Fukui, Bunkyo 3-9-1, Fukui 910-8507, Japan
    • 5Photon Factory and Condensed Matter Research Center, Institute of Materials Structure Science, High Energy Accelerator Research Organization, Oho 1-1, Tsukuba 305-0801, Japan
    • 6Laboratory for Materials and Structures, Tokyo Institute of Technology, Nagatsuta 4259, Midori, Yokohama 226-8503, Japan
    • 7Kanagawa Institute of Industrial Science and Technology (KISTEC), Ebina 243-0435, Japan

    Phys. Rev. Materials 5, 104405 – Published 13 October, 2021

    DOI: https://doi.org/10.1103/PhysRevMaterials.5.104405

    Abstract

    Henmilite {Ca2Cu(OH)4[B(OH)4]2} is a blue calcium copper borate mineral found only in the Fuka mine, Okayama Prefecture, Japan. Crystal structure refinement, magnetic and specific heat measurements, and density functional theory (DFT) calculations are performed to clarify its magnetic properties. Synchrotron x-ray diffraction experiments reveal that the hydrogen-bonded chains are arranged in an antiferroelectric manner, doubling the unit cell along the a axis. An antiferromagnetic transition is observed at 0.2 K at zero magnetic field. Furthermore, a dome-shaped antiferromagnetic ordering region exists in the temperature–magnetic-field phase diagram, indicating the presence of quantum spin fluctuations. The obtained crystal structure in combination with DFT calculations suggests that the system has a coupled two-leg ladder magnetic lattice, explaining the very low ordering temperature.

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