Electronic origins of the giant volume collapse in the pyrite mineral MnS2

Research output: Contribution to journalJournal article – Annual report year: 2019Researchpeer-review

  • Author: Durkee, Dylan

    University of Nevada Las Vegas

  • Author: Smith, Dean

    University of Nevada Las Vegas

  • Author: Torchio, Raffaella

    European Synchrotron Radiation Facility

  • Author: Petitgirard, Sylvain

    University of Bayreuth

  • Author: Briggs, Richard

    Lawrence Livermore National Laboratory

  • Author: Kantor, Innokenty

    Neutrons and X-rays for Materials Physics, Department of Physics, Technical University of Denmark, Fysikvej, 2800, Kgs. Lyngby, Denmark

  • Author: Evans, Shaun R.

    European Synchrotron Radiation Facility

  • Author: Chatterji, Tapan

    Institut Laue-Langevin

  • Author: Irifune, Tetsuo

    Ehime University

  • Author: Pascarelli, Sakura

    European Synchrotron Radiation Facility

  • Author: Lawler, Keith V.

    University of Nevada Las Vegas

  • Author: Salamat, Ashkan

    University of Nevada Las Vegas

  • Author: Kimber, Simon A.J.

    Oak Ridge National Laboratory

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The pyrite mineral MnS2 was recently shown to undergo a giant pressure-induced volume collapse at ∼ 12 GPa, via a disordered intermediate phase. The high pressure arsenopyrite phase is stabilised by metal-metal bonding, a mechanism now shown to be ubiquitous for Mn2+ chalcogenides. Here we report a spectroscopic investigation of this transition up to pressures of 22 GPa. Using XANES we show that the transition does not involve a change in oxidation state, consistent with the arsenopyrite crystal structure proposed at high pressure. Notably, the XANES spectrum is almost identical in the pressure-induced disordered phase, and after crystallisation induced by laser-heating. The former is therefore a ‘valence bond glass’, and is likely disordered due to kinetic hindrance of the phase transition. We also detect electronic changes in the compressed pyrite phase, and this is confirmed by Raman scattering which shows that the disulphide vibrations in the pyrite phase saturate before the volume collapse. Together with detailed DFT calculations, these results indicate that electronic changes precede valence bond formation between the Mn2+ cations.

Original languageEnglish
JournalJournal of Solid State Chemistry
Volume269
Pages (from-to)540-546
Number of pages7
ISSN0022-4596
DOIs
Publication statusPublished - 2019
CitationsWeb of Science® Times Cited: No match on DOI

    Research areas

  • Magnetism, Pressure, Pyrite, Spin-state transition
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