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

Dylan Durkee, Dean Smith, Raffaella Torchio, Sylvain Petitgirard, Richard Briggs, Innokenty Kantor, Shaun R. Evans, Tapan Chatterji, Tetsuo Irifune, Sakura Pascarelli, Keith V. Lawler, Ashkan Salamat, Simon A.J. Kimber*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

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

Keywords

  • Magnetism
  • Pressure
  • Pyrite
  • Spin-state transition

Cite this

Durkee, D., Smith, D., Torchio, R., Petitgirard, S., Briggs, R., Kantor, I., ... Kimber, S. A. J. (2019). Electronic origins of the giant volume collapse in the pyrite mineral MnS2. Journal of Solid State Chemistry, 269, 540-546. https://doi.org/10.1016/j.jssc.2018.10.032
Durkee, Dylan ; Smith, Dean ; Torchio, Raffaella ; Petitgirard, Sylvain ; Briggs, Richard ; Kantor, Innokenty ; Evans, Shaun R. ; Chatterji, Tapan ; Irifune, Tetsuo ; Pascarelli, Sakura ; Lawler, Keith V. ; Salamat, Ashkan ; Kimber, Simon A.J. / Electronic origins of the giant volume collapse in the pyrite mineral MnS2. In: Journal of Solid State Chemistry. 2019 ; Vol. 269. pp. 540-546.
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title = "Electronic origins of the giant volume collapse in the pyrite mineral MnS2",
abstract = "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.",
keywords = "Magnetism, Pressure, Pyrite, Spin-state transition",
author = "Dylan Durkee and Dean Smith and Raffaella Torchio and Sylvain Petitgirard and Richard Briggs and Innokenty Kantor and Evans, {Shaun R.} and Tapan Chatterji and Tetsuo Irifune and Sakura Pascarelli and Lawler, {Keith V.} and Ashkan Salamat and Kimber, {Simon A.J.}",
year = "2019",
doi = "10.1016/j.jssc.2018.10.032",
language = "English",
volume = "269",
pages = "540--546",
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issn = "0022-4596",
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Durkee, D, Smith, D, Torchio, R, Petitgirard, S, Briggs, R, Kantor, I, Evans, SR, Chatterji, T, Irifune, T, Pascarelli, S, Lawler, KV, Salamat, A & Kimber, SAJ 2019, 'Electronic origins of the giant volume collapse in the pyrite mineral MnS2', Journal of Solid State Chemistry, vol. 269, pp. 540-546. https://doi.org/10.1016/j.jssc.2018.10.032

Electronic origins of the giant volume collapse in the pyrite mineral MnS2. / Durkee, Dylan; Smith, Dean; Torchio, Raffaella; Petitgirard, Sylvain; Briggs, Richard; Kantor, Innokenty; Evans, Shaun R.; Chatterji, Tapan; Irifune, Tetsuo; Pascarelli, Sakura; Lawler, Keith V.; Salamat, Ashkan; Kimber, Simon A.J.

In: Journal of Solid State Chemistry, Vol. 269, 2019, p. 540-546.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Electronic origins of the giant volume collapse in the pyrite mineral MnS2

AU - Durkee, Dylan

AU - Smith, Dean

AU - Torchio, Raffaella

AU - Petitgirard, Sylvain

AU - Briggs, Richard

AU - Kantor, Innokenty

AU - Evans, Shaun R.

AU - Chatterji, Tapan

AU - Irifune, Tetsuo

AU - Pascarelli, Sakura

AU - Lawler, Keith V.

AU - Salamat, Ashkan

AU - Kimber, Simon A.J.

PY - 2019

Y1 - 2019

N2 - 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.

AB - 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.

KW - Magnetism

KW - Pressure

KW - Pyrite

KW - Spin-state transition

U2 - 10.1016/j.jssc.2018.10.032

DO - 10.1016/j.jssc.2018.10.032

M3 - Journal article

VL - 269

SP - 540

EP - 546

JO - Journal of Solid State Chemistry

JF - Journal of Solid State Chemistry

SN - 0022-4596

ER -