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

Abstract: 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 $\sim$45 GPa, accompanied by anomalous changes of this mineral's physical properties, while the intermediate-spin ($S=1$) state has not been observed. In this work, we investigate (Mg${1-x}$Fe$x$)O ($x \leq 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 $\sim$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.