Pressure-induced redox reversal of iron and the distribution of elements in deep Earth

We demonstrate a remarkable change in the chemical bonding of iron under pressure that underlies the distribution of elements in the Earth's mantle and core. Using a massive-scale, first-principles study, we show that while reacting with <i>p</i>-block elements under increasing pressure from ambient to Earth core conditions, iron tends to reverse its redox nature, changing from an electron donor (reductant) to an electron acceptor (oxidant), and oxidizes many <i>p</i>-block elements. Such reverse redox propensity significantly impacts the stoichiometries, bond types and strengths, structures, and properties of iron compounds under deep planetary conditions. This change transforms many <i>p-</i>block elements (conventionally labeled lithophile or chalcophile) into highly siderophile species. The chemical binding strengths with iron show an inverse correlation with the depletion of <i>p</i>-block elements in the silicate Earth. Furthermore, silicon shows a distinct anomaly in its bonding to iron, which suggests silicon may readily be incorporated into Earth's core.

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Publication Details

Journal
Proceedings of the National Academy of Sciences
Published
2025-11-10
DOI
https://doi.org/10.1073/pnas.2414911122
Citations
1
Primary Topic
High-pressure geophysics and materials
Type
article
Field-Weighted Citation Impact
1.87
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Pressure-induced redox reversal of iron and the distribution of elements in deep Earth

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Pressure-induced redox reversal of iron and the distribution of elements in deep Earth

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article en
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Abstract

We demonstrate a remarkable change in the chemical bonding of iron under pressure that underlies the distribution of elements in the Earth's mantle and core. Using a massive-scale, first-principles study, we show that while reacting with <i>p</i>-block elements under increasing pressure from ambient to Earth core conditions, iron tends to reverse its redox nature, changing from an electron donor (reductant) to an electron acceptor (oxidant), and oxidizes many <i>p</i>-block elements. Such reverse redox propensity significantly impacts the stoichiometries, bond types and strengths, structures, and properties of iron compounds under deep planetary conditions. This change transforms many <i>p-</i>block elements (conventionally labeled lithophile or chalcophile) into highly siderophile species. The chemical binding strengths with iron show an inverse correlation with the depletion of <i>p</i>-block elements in the silicate Earth. Furthermore, silicon shows a distinct anomaly in its bonding to iron, which suggests silicon may readily be incorporated into Earth's core.

Proceedings of the National Academy of SciencesVol. 122(46)
California State University System (US), University of California, Santa Barbara (US), California State University, Northridge (US), University of Illinois Urbana-Champaign (US), Nanyang Technological University (SG), Yantai University (CN), University of Illinois Chicago (US)
Openalex Percentile: Top 13%
High-pressure geophysics and materials
1.87
DOIOpen Access PDFOpenAlex
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