Intermediate spin state and the B1-B2 transition in ferropericlase at tera-Pascal pressures

Abstract: Ferropericlase (fp), (Mg${1-x}$Fe$_x$)O, the second most abundant mineral in the Earth's lower mantle, is expected to be an essential component of super-Earths' mantles. Here we present an ab initio investigation of the structure and magnetic ground state of fp up to $\sim$ 3 TPa with iron concentrations (x${Fe}$) varying from 0.03 to 0.12. Calculations were performed using LDA+U${sc}$ and PBE exchange-correlation functionals to elucidate the pressure range for which the Hubbard U (U${sc}$) is required. Similar to the end-members FeO and MgO, fp also undergoes a B1 to B2 phase transition that should be essential for modeling the structure and dynamics of super-Earths' mantles. This structural transition involves a simultaneous change in magnetic state from a low spin (LS) B1 phase with iron total spin S=0 to an intermediate spin (IS) B2 phase with S=1. This is a rare form of pressure/strain-induced magnetism produced by local cation coordination changes. Phonon calculations confirm the dynamical stability of the iron B2-IS state. Free energy calculations are then carried out including vibrational effects and electronic and magnetic entropy contributions. The phase diagram is then obtained for low concentration fp using a quasi-ideal solid solution model. For x${Fe}$ > 0.12 this approach is no longer valid. At ultra-high pressures, there is an IS to LS spin state change in Fe in the B2 phase, but the transition pressure depends sensitively on thermal electronic excitations and on x${Fe}$.