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Crystal-structure properties and the molecular nature of hydrostatically compressed realgar

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Abstract

The structure of realgar, As4S4, and its evolution with pressure have been investigated employing in situ X-ray diffraction, optical absorption and vibrational spectroscopy on single-crystal samples in diamond-anvil cells. Compression under true hydrostatic conditions up to 5.40 GPa reveals equation-of-state parameters of V 0 = 799.4(2.4) Å3 and K 0 = 10.5(0.4) GPa with \(K_0^\prime\) = 8.7. The remarkably high compressibility can be attributed to a denser packing of the As4S4 molecules with shortening of the intermolecular bonds of up to 12 %, while the As4S4 molecules remain intact showing rigid-unit behaviour. From ambient pressure to 4.5 GPa, Raman spectra exhibit a strong blue shift of the Raman bands of the lattice-phonon regime of 24 cm–1, whereas frequencies from intramolecular As-S stretching modes show negligible or no shifts at all. On pressurisation, realgar shows a continuous and reversible colour change from bright orange over deep red to black. Optical absorption spectroscopy shows a shift of the absorption edge from 2.30 to 1.81 eV up to 4.5 GPa, and DFT calculations show a corresponding reduction in the band gap. Synchrotron-based measurements on polycrystalline samples up to 45.5 GPa are indexed according to the monoclinic structure of realgar.

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Acknowledgments

We acknowledge the possibility to carry out powder diffraction measurements within the scope of project HS-3821 at beamline ID27 at the European Synchrotron Radiation Facility, ESRF, Grenoble. In particular, we thank Wilson Crichton, Pascal Schouwink and Robert Klein for their technical assistance. L.N. acknowledges funding by the European Commission through contract no. MEXC-CT-2005-024878. C.H. acknowledges funding by the “Nachwuchsförderung” of the University of Innsbruck. T.BZ. acknowledges funding by a grant from the Danish Agency for Science, Technology and Innovation. Constructive reviews from L. Bindi and an anonymous referee contributed to improve the manuscript.

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Authors and Affiliations

  1. Mineralogy and Petrography, University of Innsbruck, 6020, Innsbruck, Austria

    Clivia Hejny

  2. Voestalpine Stahl GmbH, 4031, Linz, Austria

    Raffaela Sagl

  3. Helmholtz-Zentrum Berlin für Materialien und Energie, 14109, Berlin, Germany

    Daniel M. Többens

  4. Institute for Mineralogy and Crystallography, University of Vienna, 1090, Vienna, Austria

    Ronald Miletich, Manfred Wildner & Lutz Nasdala

  5. Institute for Technology of Karlsruhe (KIT), 76344, Eggenstein Leopoldshafen, Germany

    Angela Ullrich

  6. Natural History Museum of Denmark, University of Copenhagen, 1350, Copenhagen, Denmark

    Tonci Balic-Zunic

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  1. Clivia Hejny
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Correspondence to Clivia Hejny.

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Hejny, C., Sagl, R., Többens, D.M. et al. Crystal-structure properties and the molecular nature of hydrostatically compressed realgar. Phys Chem Minerals 39, 399–412 (2012). https://doi.org/10.1007/s00269-012-0495-y

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