Giant pressure-induced volume collapse in the pyrite mineral MnS 2

Simon A J Kimber, Ashkan Salamat, Shaun R. Evans, Harald Olaf Jeschke, Kaliappan Muthukumar, Milan Tomic, Francesc Salvat-Pujol, Roser Valentí, Maria V. Kaisheva, Ivo Zizak, Tapan Chatterji

Research output: Contribution to journalArticle

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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 spinstate transitions, the interplay between the single-ion crystal field and the size of the magnetic moment. Here we show that the classical S=52 mineral hauerite (MnS2) undergoes an unprecedented (ΔV∼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=12 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.

Original languageEnglish
Pages (from-to)5106-5110
Number of pages5
JournalProceedings of the National Academy of Sciences of the United States of America
Volume111
Issue number14
DOIs
Publication statusPublished - 2014
Externally publishedYes

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pyrites
minerals
metal-metal bonding
laser heating
geochemistry
dimerization
crystal field theory
synchrotrons
superconductivity
magnetic moments
transition metals
moments
thermodynamics
ground state
hydrogen
diffraction
ions
x rays

ASJC Scopus subject areas

  • General

Cite this

Giant pressure-induced volume collapse in the pyrite mineral MnS 2. / Kimber, Simon A J; Salamat, Ashkan; Evans, Shaun R.; Jeschke, Harald Olaf; Muthukumar, Kaliappan; Tomic, Milan; Salvat-Pujol, Francesc; Valentí, Roser; Kaisheva, Maria V.; Zizak, Ivo; Chatterji, Tapan.

In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 111, No. 14, 2014, p. 5106-5110.

Research output: Contribution to journalArticle

Kimber, SAJ, Salamat, A, Evans, SR, Jeschke, HO, Muthukumar, K, Tomic, M, Salvat-Pujol, F, Valentí, R, Kaisheva, MV, Zizak, I & Chatterji, T 2014, 'Giant pressure-induced volume collapse in the pyrite mineral MnS 2', Proceedings of the National Academy of Sciences of the United States of America, vol. 111, no. 14, pp. 5106-5110. https://doi.org/10.1073/pnas.1318543111
Kimber, Simon A J ; Salamat, Ashkan ; Evans, Shaun R. ; Jeschke, Harald Olaf ; Muthukumar, Kaliappan ; Tomic, Milan ; Salvat-Pujol, Francesc ; Valentí, Roser ; Kaisheva, Maria V. ; Zizak, Ivo ; Chatterji, Tapan. / Giant pressure-induced volume collapse in the pyrite mineral MnS 2. In: Proceedings of the National Academy of Sciences of the United States of America. 2014 ; Vol. 111, No. 14. pp. 5106-5110.
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AU - Salamat, Ashkan

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AU - Tomic, Milan

AU - Salvat-Pujol, Francesc

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AB - 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 spinstate transitions, the interplay between the single-ion crystal field and the size of the magnetic moment. Here we show that the classical S=52 mineral hauerite (MnS2) undergoes an unprecedented (ΔV∼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=12 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.

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