Spin and valence states of iron in (Mg[subscript 0.8]Fe[subscript 0.2])SiO[subscript 3] perovskite

• Main Authors: Grocholski, Brent (Contributor), Shim, Sang-Heon Dan (Contributor), Sturhahn, W. (Author), Zhao, J. (Author), Xiao, Y. (Author), Chow, P. C. (Author)
• Other Authors: Massachusetts Institute of Technology. Department of Earth, Atmospheric, and Planetary Sciences (Contributor), Shim, Sang-Heon (Contributor)
• Format: Article
• Language: English
• Published: American Geophysical Union, 2011-01-13T21:00:22Z.
• Subjects: Article
• Online Access: Get fulltext

The spin and valence states of iron in (Mg0.8Fe0.2)SiO3 perovskite were measured between 0 and 65 GPa using synchrotron Mössbauer spectroscopy. Samples were synthesized in situ in the laser-heated diamond cell under reducing conditions. The dominant spin state of iron in perovskite is high spin at pressures below 50 GPa. Above 50 GPa, the spectra shows severe changes which can be explained by appearance of two distinct iron sites with similar site weightings. One site has Mössbauer parameters consistent with high spin Fe2+, while the other has the parameters previously interpreted as intermediate spin. The latter intermediate-spin assignment is not unique, as similar Mössbauer parameters have been reported for high spin Fe2+ in almandine at ambient pressure. However, our data do not rule out the existence of low-spin iron, which may exist with a smaller fraction and explain the observation of lower spin moments in the X-ray emission spectroscopy of perovskite at high pressure. From these considerations, our preferred interpretation is that iron in perovskite is mixed or high spin to at least 2000 km depths in the mantle, consistent with computational results. Our study also reveals that reducing conditions do not inhibit the formation of Fe3+ in perovskite at deep-mantle pressures.
United States. Dept. of Energy. Office of Basic Energy Sciences
United States. National Nuclear Security Administration
National Science Foundation (U.S.) (EAR0738655)
United States. Dept of Energy (DE-AC02-06CH11357)
W. M. Keck Foundation