Effect of dilution on the spin pairing transition in rhombohedral carbonates

The compressibility of an iron-bearing magnesite was determined by means of single crystal diffraction up to 64 GPa. Up to 49 GPa the pressure-evolution of the unit cell volume of the solid solution with 12% of Fe2+ can be described by a third-order Birch–Murnaghan equation of state with parameters V 0=281.0(5) Å3, K 0=102.8(3) GPa, K. The spin pairing of the Fe2+ d-electrons occurs between 49 and 52 GPa, as evidenced by a discontinuous volume change. The transition pressure is increased by about 5 GPa compared with the iron end-member; an effect consistent with a cooperative contribution of adjacent clusters to the spin transition. The trend is, however, opposite in the periclase–wüstite solid solution. Differences among the two structures, in particular in the Fe–Fe interactions, that might explain the different behavior are discussed.