Phonon dispersions throughout the iron spin crossover in ferropericlase

Abstract

Ferropericlase (Fp), (Mg${}_{1-\mathrm{x}}$Fe${}_{\mathrm{x}}$)O, is the second most abundant phase in the Earths lower mantle. At relevant pressure-temperature conditions, iron in Fp undergoes a high spin (HS), S=2, to low spin (LS), S=0, state change. The nature of this phenomenon is quite well understood now, but there are still basic questions regarding the structural stability and the existence of soft phonon modes during this iron state change. General theories exist to explain the volume reduction, the significant thermo-elastic anomalies, and the broad nature of this HS-LS crossover. These theories make extensive use of the quasi-harmonic approximation (QHA). Therefore, dynamical and structural stability is essential to their validity. Here, we investigate the vibrational spectrum of Fp throughout this spin-crossover using $\text{ab initio}$ DFT+Usc calculations. We address vibrational modes associated with isolated and (2nd) nearest neighbor iron ions undergoing the HS-LS state change. As expected, acoustic modes of this solid solution are resilient while optical modes are the most affected. We show that there are no soft phonon modes across this HS-LS crossover, and Fp is dynamically stable at all relevant pressures.

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• Phase transitions and spin-state of iron in FeO at the conditions of Earth's deep interior
• Thermodynamics of spin crossover in ferropericlase: an improved LDA+$U_{sc}$ calculation
• Intermediate spin state and the B1-B2 transition in ferropericlase at tera-Pascal pressures
• Two state model for critical points and the negative slope of the melting-curve