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The Spin state of iron in Fe$$^{3+}$$-bearing Mg-perovskite and its crystal chemistry at high pressure

Mashimo, Izumi*; Otani, Eiji*; Hirao, Naohisa*; Mitsui, Takaya; Masuda, Ryo*; Seto, Makoto*; Sakai, Takeshi*; Takahashi, Suguru*; Nakano, Satoshi*

Valence, spin states, and crystallographic sites of Fe in (Mg,Fe)SiO$$_{3}$$ perovskite were investigated using energy-domain $$^{57}$$Fe-synchrotron M$"o$ssbauer spectroscopy and powder X-ray diffraction up to 86 GPa. The volumes of Fe$$^{3+}$$ bearing perovskite in this study are slightly smaller than those of Mg endmember perovskite. Our M$"o$ssbauer data suggest that Fe$$^{3+}$$ prefers A sites coupled with Mg vacancies, which is consistent with previous data at ambient conditions. Fe$$^{3+}$$ in the A site remains in a high spin state up to 86 GPa, and some fraction of the A site is occupied by Fe$$^{2+}$$ at pressures above 30 GPa. Fe$$^{2+}$$ in the A sites is also in a high spin state up to 86 GPa. The coupled substitution from Mg$$^{2+}$$ to a high spin state of Fe$$^{3+}$$ and Mg$$^{2+}$$ vacancy would make the volume of perovskite smaller than that of Mg endmember perovskite.

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Category:Geochemistry & Geophysics

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