skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

This content will become publicly available on July 15, 2020

Title: Electronic spin transition in FeO 2 : Evidence for Fe(II) with peroxide O 2 2

Abstract

The discovery of FeO 2 containing more oxygen than hematite (Fe 2O 3), which was previously believed to be the most oxygen rich iron compound, has important implications for the study of deep lower mantle compositions. Compared to other iron compounds, there are limited reports on FeO 2, making studies of its physical properties of great interest in fundamental condensed matter physics and geoscience. Even the oxidation state of Fe in FeO 2 is the subject of debate in theoretical works and there have not been reports from experimental electronic and magnetic properties measurements. Here, we report the pressure-induced spin state transition from synchrotron experiments and our computational results explain the underlying mechanism. Using density functional theory and dynamical mean field theory, we calculated spin states of Fe with volume and Hubbard interaction U change, which clearly demonstrate that Fe in FeO 2 consists of Fe(II) and peroxide O 2– 2. In conclusion, our paper suggests that the localized nature of both Fe 3d orbitals and O 2 molecular orbitals should be correctly treated for unveiling the structural and electronic properties of FeO 2.

Authors:
 [1];  [2];  [3];  [4];  [3];  [5];  [6];  [1]
  1. Pohang Univ. of Science and Technology, Pohang (Korea)
  2. Stanford Univ., Stanford, CA (United States)
  3. Center for High Pressure Science and Technology Advanced Research, Shanghai (China)
  4. Rutgers Univ., Piscataway, NJ (United States)
  5. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  6. Center for High Pressure Science and Technology Advanced Research, Shanghai (China); Pohang University of Science and Technology, Pohang (Korea)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1546707
Grant/Contract Number:  
AC02-76SF00515; 2015R1A2A1A15051540; NRF-2017R1D1A1B03031913; KSC-2016-C1-0003; 11774015; EAR 1446969; NSF-DMREF 1709229
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 100; Journal Issue: 1; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English

Citation Formats

Jang, Bo Gyu, Liu, Jin, Hu, Qingyang, Haule, Kristjan, Mao, Ho -Kwang, Mao, Wendy L., Kim, Duck Young, and Shim, Ji Hoon. Electronic spin transition in FeO2 : Evidence for Fe(II) with peroxide O22–. United States: N. p., 2019. Web. doi:10.1103/physrevb.100.014418.
Jang, Bo Gyu, Liu, Jin, Hu, Qingyang, Haule, Kristjan, Mao, Ho -Kwang, Mao, Wendy L., Kim, Duck Young, & Shim, Ji Hoon. Electronic spin transition in FeO2 : Evidence for Fe(II) with peroxide O22–. United States. doi:10.1103/physrevb.100.014418.
Jang, Bo Gyu, Liu, Jin, Hu, Qingyang, Haule, Kristjan, Mao, Ho -Kwang, Mao, Wendy L., Kim, Duck Young, and Shim, Ji Hoon. Mon . "Electronic spin transition in FeO2 : Evidence for Fe(II) with peroxide O22–". United States. doi:10.1103/physrevb.100.014418.
@article{osti_1546707,
title = {Electronic spin transition in FeO2 : Evidence for Fe(II) with peroxide O22–},
author = {Jang, Bo Gyu and Liu, Jin and Hu, Qingyang and Haule, Kristjan and Mao, Ho -Kwang and Mao, Wendy L. and Kim, Duck Young and Shim, Ji Hoon},
abstractNote = {The discovery of FeO2 containing more oxygen than hematite (Fe2O3), which was previously believed to be the most oxygen rich iron compound, has important implications for the study of deep lower mantle compositions. Compared to other iron compounds, there are limited reports on FeO2, making studies of its physical properties of great interest in fundamental condensed matter physics and geoscience. Even the oxidation state of Fe in FeO2 is the subject of debate in theoretical works and there have not been reports from experimental electronic and magnetic properties measurements. Here, we report the pressure-induced spin state transition from synchrotron experiments and our computational results explain the underlying mechanism. Using density functional theory and dynamical mean field theory, we calculated spin states of Fe with volume and Hubbard interaction U change, which clearly demonstrate that Fe in FeO2 consists of Fe(II) and peroxide O2–2. In conclusion, our paper suggests that the localized nature of both Fe 3d orbitals and O2 molecular orbitals should be correctly treated for unveiling the structural and electronic properties of FeO2.},
doi = {10.1103/physrevb.100.014418},
journal = {Physical Review B},
number = 1,
volume = 100,
place = {United States},
year = {2019},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on July 15, 2020
Publisher's Version of Record

Save / Share:

Works referenced in this record:

Metal-insulator transitions
journal, October 1998

  • Imada, Masatoshi; Fujimori, Atsushi; Tokura, Yoshinori
  • Reviews of Modern Physics, Vol. 70, Issue 4, p. 1039-1263
  • DOI: 10.1103/RevModPhys.70.1039

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976