Structural transition and re-emergence of iron's total electron spin in (Mg,Fe)O at ultrahigh pressure

Fe-bearing MgO [(Mg 1− x Fe x )O] is considered a major constituent of terrestrial exoplanets. Crystallizing in the B1 structure in the Earth’s lower mantle, (Mg 1− x Fe x )O undergoes a high-spin ( S = 2) to low-spin ( S = 0) transition at ∼45 GPa, accompanied by anomalous changes of this mineral’s physical properties, while the intermediate-spin ( S = 1) state has not been observed. In this work, we investigate (Mg 1− x Fe x )O ( x ≤ 0.25) up to 1.8 TPa via first-principles calculations. Our calculations indicate that (Mg 1− x Fe x )O undergoes a simultaneous structural and spin transition at ∼0.6 TPa, from the B1 phase low-spin state to the B2 phase intermediate-spin state, with Fe’s total electron spin S re-emerging from 0 to 1 at ultrahigh pressure. Upon further compression, an intermediate-to-low spin transition occurs in the B2 phase. Depending on the Fe concentration ( x ), metal–insulator transition and rhombohedral distortions can also occur in the B2 phase. These results suggest that Fe and spin transition may affect planetary interiors over a vast pressure range.