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Giant pressure-induced volume collapse in the pyrite mineral MnS2.


ABSTRACT: Dramatic volume collapses under pressure are fundamental to geochemistry and of increasing importance to fields as diverse as hydrogen storage and high-temperature superconductivity. In transition metal materials, collapses are usually driven by so-called spin-state transitions, the interplay between the single-ion crystal field and the size of the magnetic moment. Here we show that the classical S = 5/2 mineral hauerite (MnS2) undergoes an unprecedented (?V ~ 22%) collapse driven by a conceptually different magnetic mechanism. Using synchrotron X-ray diffraction we show that cold compression induces the formation of a disordered intermediate. However, using an evolutionary algorithm we predict a new structure with edge-sharing chains. This is confirmed as the thermodynamic ground state using in situ laser heating. We show that magnetism is globally absent in the new phase, as low-spin quantum S = 1/2 moments are quenched by dimerization. Our results show how the emergence of metal-metal bonding can stabilize giant spin-lattice coupling in Earth's minerals.

SUBMITTER: Kimber SA 

PROVIDER: S-EPMC3986163 | biostudies-literature | 2014 Apr

REPOSITORIES: biostudies-literature

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Giant pressure-induced volume collapse in the pyrite mineral MnS2.

Kimber Simon A J SA   Salamat Ashkan A   Evans Shaun R SR   Jeschke Harald O HO   Muthukumar Kaliappan K   Tomić Milan M   Salvat-Pujol Francesc F   Valentí Roser R   Kaisheva Maria V MV   Zizak Ivo I   Chatterji Tapan T  

Proceedings of the National Academy of Sciences of the United States of America 20140324 14


Dramatic volume collapses under pressure are fundamental to geochemistry and of increasing importance to fields as diverse as hydrogen storage and high-temperature superconductivity. In transition metal materials, collapses are usually driven by so-called spin-state transitions, the interplay between the single-ion crystal field and the size of the magnetic moment. Here we show that the classical S = 5/2 mineral hauerite (MnS2) undergoes an unprecedented (ΔV ~ 22%) collapse driven by a conceptua  ...[more]

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