Synchrotron Mössbauer spectroscopic study of ferropericlase at high pressures and temperatures
Abstract
The electronic spin state of Fe^(2+) in ferropericlase, (Mg_(0.75)Fe_(0.25))O, transitions from a high-spin (spin unpaired) to low-spin (spin paired) state within the Earth's mid-lower mantle region. To better understand the local electronic environment of high-spin Fe^(2+) ions in ferropericlase near the transition, we obtained synchrotron Mössbauer spectra (SMS) of (Mg_(0.75),Fe_(0.25))O in externally heated and laser-heated diamond anvil cells at relevant high pressures and temperatures. Results show that the quadrupole splitting (QS) of the dominant high-spin Fe^(2+) site decreases with increasing temperature at static high pressure. The QS values at constant pressure are fitted to a temperature-dependent Boltzmann distribution model, which permits estimation of the crystal-field splitting energy (Δ_3) between the d_(xy_ and d_(xz) or d_(zy) orbitals of the t_(2g) states in a distorted octahedral Fe^(2+) site. The derived Δ_3 increases from approximately 36 meV at 1 GPa to 95 meV at 40 GPa, revealing that both high pressure and high temperature have significant effects on the 3d electronic shells of Fe^(2+) in ferropericlase. The SMS spectra collected from the laser-heated diamond cells within the time window of 146 ns also indicate that QS significantly decreases at very high temperatures. A larger splitting of the energy levels at high temperatures and pressures should broaden the spin crossover in ferropericlase because the degeneracy of energy levels is partially lifted. Our results provide information on the hyperfine parameters and crystal-field splitting energy of high-spin Fe^(2+) in ferropericlase at high pressures and temperatures, relevant to the electronic structure of iron in oxides in the deep lower mantle.
Additional Information
© 2009 Mineralogical Society of America. Manuscript received OctOber 7, 2008. Manuscript accepted nOveMber 22, 2008. Manuscript handled by M. Darby Dyar. Experiments were performed at sectors 16 (HPCAT) and 3 (XOR-3) of the Advanced Photon Source, Argonne National Laboratory. Use of the APS was supported by U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, under contract DE-AC02-06CH11357. J.F.L. acknowledges support from the U.S. National Science Foundation (EAR-0838221) and the Carnegie/ DOE Alliance Center (CDAC). A.G.G. is supported by Russian Foundation for Basic Research grants, 07-02-00490-а, and 08-02-00897-а, and by the Program of Physical Branch of the Russian Academy of Sciences under the project of "Strong Correlating Electron Systems." S.D.J. acknowledges support from the US National Science Foundation (EAR-0721449) and the Carnegie/DOE Alliance Center (CDAC). This research was partially supported by COMPRES, the Consortium for Materials Properties Research in Earth Sciences under NSF Cooperative Agreement EAR 06-49658.Attached Files
Published - Lin2009p2081Am_Mineral.pdf
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Additional details
- Eprint ID
- 15744
- Resolver ID
- CaltechAUTHORS:20090910-150634682
- U.S. Department of Energy
- Office of Science
- DE-AC02-06CH11357
- Basic Energy Sciences
- EAR-0838221
- NSF
- Carnegie Department of Energy Alliance Center
- 07-02-00490-а
- Russian Foundation for Basic Research
- 08-02-00897-а
- Russian Foundation for Basic Research
- Program of Physical Branch of the Russian Academy of Sciences
- EAR-0721449
- NSF
- Carnegie Department of Energy Alliance Center
- EAR 06-49658
- NSF Cooperative Agreement
- Created
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2009-09-14Created from EPrint's datestamp field
- Updated
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2021-11-08Created from EPrint's last_modified field