Resonant X-ray emission study of the lower-mantle ferropericlase at high pressures

Jung Fu Lin, Zhu Mao, Ignace Jarrige, Yuming Xiao, Paul Chow, Takuo Okuchi, Nozomu Hiraoka, Steven D. Jacobsen

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

Electronic states of iron in Earth's mantle minerals including ferropericlase, silicate perovskite, and post-perovskite have been previously investigated at high pressures and/or temperatures using various experimental techniques, including X-ray emission and Mössbauer spectroscopies. Although such methods have been used to infer changes in the electronic spin and valence states of iron in lower mantle minerals, they do not directly probe the 3d electronic states quantitatively. Here we use 1s2p resonant X-ray emission spectroscopy (RXES) at the Fe K pre-edge to directly probe and assess the 3d electronic states and the crystal-field splittings of Fe2+ in the lower-mantle ferropericlase [(Mg0.75,Fe0.25)O] at pressures up to 90 GPa. The pre-edge features from X-ray absorptionspectroscopy in the partial fluorescence yield (PFY-XAS) and RXES results explicitly show three excited states for high-spin Fe2+ (a lower-energy 4T1g state, a 4T2g state, and a higher-energy 4T1g state) and a single 2E g state for low-spin Fe2+, attributed to the (t 2g)0(eg)3 excited configuration. This latter feature begins to appear at 48 GPa and grows with pressure, while the peaks related to high-spin Fe2+ vanish above 80 GPa. The observed pre-edge features are consistent with purely quadrupolar transitions resultingfrom the centrosymmetric character of the Fe2+ site. The Kpre-edge RXES spectra at the incident energy of 7112 eV, which are similar to the Fe L-edge spectra, are also used successfully to quantitatively obtain consistent results on the spin transition of Fe2+ in ferropericlase under high pressures. Owing to the superior sensitivity of the RXES technique, the observed electronic states andtheir energy separations provide direct information on the local electronic structures and crystal-field splitting energies of the 3d electronic shells of Fe2+ in ferropericlase at relevant pressures of the Earth's lower mantle.

Original languageEnglish
Pages (from-to)1125-1131
Number of pages7
JournalAmerican Mineralogist
Volume95
Issue number8-9
DOIs
Publication statusPublished - Aug 2010

Fingerprint

lower mantle
Electronic states
Earth mantle
X rays
spectroscopy
electronics
x rays
Electron energy levels
Minerals
perovskite
energy
Iron
Earth (planet)
crystal field theory
Silicates
Crystals
minerals
iron
probe
crystal

Keywords

  • Diamond anvil cell
  • Ferropericlase
  • High pressures
  • Partial fluorescence yield
  • Resonant X-rayemission spectroscopy
  • Spin transition

ASJC Scopus subject areas

  • Geochemistry and Petrology
  • Geophysics

Cite this

Lin, J. F., Mao, Z., Jarrige, I., Xiao, Y., Chow, P., Okuchi, T., ... Jacobsen, S. D. (2010). Resonant X-ray emission study of the lower-mantle ferropericlase at high pressures. American Mineralogist, 95(8-9), 1125-1131. https://doi.org/10.2138/am.2010.3495

Resonant X-ray emission study of the lower-mantle ferropericlase at high pressures. / Lin, Jung Fu; Mao, Zhu; Jarrige, Ignace; Xiao, Yuming; Chow, Paul; Okuchi, Takuo; Hiraoka, Nozomu; Jacobsen, Steven D.

In: American Mineralogist, Vol. 95, No. 8-9, 08.2010, p. 1125-1131.

Research output: Contribution to journalArticle

Lin, JF, Mao, Z, Jarrige, I, Xiao, Y, Chow, P, Okuchi, T, Hiraoka, N & Jacobsen, SD 2010, 'Resonant X-ray emission study of the lower-mantle ferropericlase at high pressures', American Mineralogist, vol. 95, no. 8-9, pp. 1125-1131. https://doi.org/10.2138/am.2010.3495
Lin, Jung Fu ; Mao, Zhu ; Jarrige, Ignace ; Xiao, Yuming ; Chow, Paul ; Okuchi, Takuo ; Hiraoka, Nozomu ; Jacobsen, Steven D. / Resonant X-ray emission study of the lower-mantle ferropericlase at high pressures. In: American Mineralogist. 2010 ; Vol. 95, No. 8-9. pp. 1125-1131.
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abstract = "Electronic states of iron in Earth's mantle minerals including ferropericlase, silicate perovskite, and post-perovskite have been previously investigated at high pressures and/or temperatures using various experimental techniques, including X-ray emission and M{\"o}ssbauer spectroscopies. Although such methods have been used to infer changes in the electronic spin and valence states of iron in lower mantle minerals, they do not directly probe the 3d electronic states quantitatively. Here we use 1s2p resonant X-ray emission spectroscopy (RXES) at the Fe K pre-edge to directly probe and assess the 3d electronic states and the crystal-field splittings of Fe2+ in the lower-mantle ferropericlase [(Mg0.75,Fe0.25)O] at pressures up to 90 GPa. The pre-edge features from X-ray absorptionspectroscopy in the partial fluorescence yield (PFY-XAS) and RXES results explicitly show three excited states for high-spin Fe2+ (a lower-energy 4T1g state, a 4T2g state, and a higher-energy 4T1g state) and a single 2E g state for low-spin Fe2+, attributed to the (t 2g)0(eg)3 excited configuration. This latter feature begins to appear at 48 GPa and grows with pressure, while the peaks related to high-spin Fe2+ vanish above 80 GPa. The observed pre-edge features are consistent with purely quadrupolar transitions resultingfrom the centrosymmetric character of the Fe2+ site. The Kpre-edge RXES spectra at the incident energy of 7112 eV, which are similar to the Fe L-edge spectra, are also used successfully to quantitatively obtain consistent results on the spin transition of Fe2+ in ferropericlase under high pressures. Owing to the superior sensitivity of the RXES technique, the observed electronic states andtheir energy separations provide direct information on the local electronic structures and crystal-field splitting energies of the 3d electronic shells of Fe2+ in ferropericlase at relevant pressures of the Earth's lower mantle.",
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AU - Xiao, Yuming

AU - Chow, Paul

AU - Okuchi, Takuo

AU - Hiraoka, Nozomu

AU - Jacobsen, Steven D.

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N2 - Electronic states of iron in Earth's mantle minerals including ferropericlase, silicate perovskite, and post-perovskite have been previously investigated at high pressures and/or temperatures using various experimental techniques, including X-ray emission and Mössbauer spectroscopies. Although such methods have been used to infer changes in the electronic spin and valence states of iron in lower mantle minerals, they do not directly probe the 3d electronic states quantitatively. Here we use 1s2p resonant X-ray emission spectroscopy (RXES) at the Fe K pre-edge to directly probe and assess the 3d electronic states and the crystal-field splittings of Fe2+ in the lower-mantle ferropericlase [(Mg0.75,Fe0.25)O] at pressures up to 90 GPa. The pre-edge features from X-ray absorptionspectroscopy in the partial fluorescence yield (PFY-XAS) and RXES results explicitly show three excited states for high-spin Fe2+ (a lower-energy 4T1g state, a 4T2g state, and a higher-energy 4T1g state) and a single 2E g state for low-spin Fe2+, attributed to the (t 2g)0(eg)3 excited configuration. This latter feature begins to appear at 48 GPa and grows with pressure, while the peaks related to high-spin Fe2+ vanish above 80 GPa. The observed pre-edge features are consistent with purely quadrupolar transitions resultingfrom the centrosymmetric character of the Fe2+ site. The Kpre-edge RXES spectra at the incident energy of 7112 eV, which are similar to the Fe L-edge spectra, are also used successfully to quantitatively obtain consistent results on the spin transition of Fe2+ in ferropericlase under high pressures. Owing to the superior sensitivity of the RXES technique, the observed electronic states andtheir energy separations provide direct information on the local electronic structures and crystal-field splitting energies of the 3d electronic shells of Fe2+ in ferropericlase at relevant pressures of the Earth's lower mantle.

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