Anomalous thermal properties and spin crossover of ferromagnesite (Mg,Fe) CO3

Ferromagnesite $[({\mathrm{Mg}}_{1\ensuremath{-}x}{\mathrm{Fe}}_x){\mathrm{CO}}₃]$, also referred to as magnesiosiderite at high iron concentration ($x>0.5$), is a solid solution of magnesite $(\mathrm{Mg}{\mathrm{CO}}₃$) and siderite ($\mathrm{Fe}{\mathrm{CO}}₃$). Ferromagnesite is believed to enter the Earth's lower mantle via subduction and is considered a major carbon carrier in the Earth's lower mantle, playing a key role in the Earth's deep carbon cycle. Experiments have shown that ferromagnesite undergoes a pressure-induced spin crossover, accompanied by volume and elastic anomalies, in the lower-mantle pressure range. In this work, we investigate thermal properties of $({\mathrm{Mg}}_{1\ensuremath{-}x}{\mathrm{Fe}}_x){\mathrm{CO}}₃$ ($0<x\ensuremath{\le}1$) using first-principles calculations. We show that nearly all thermal properties of ferromagnesite are drastically altered by iron spin crossover, including anomalous reduction of volume, anomalous softening of bulk modulus, and anomalous increases of thermal expansion, heat capacity, and the Gr\"uneisen parameter. Remarkably, the anomaly of heat capacity remains prominent (up to $\ensuremath{\sim}40%$) at high temperature without smearing out, which suggests that iron spin crossover may significantly affect the thermal properties of subducting slabs and the Earth's deep carbon cycle.