Disordered Aragonite: The New High-Pressure, High-Temperature Phase of CaCO₃

Abstract

Phases of CaCO3 stabilized at high pressures and temperatures are the potential agents of the global carbon cycle, transferring oxidized carbon in deep Earth’s interiors and thus are of special interest for the Earth sciences. Here, we report finding of the new phase, named disarag, which is dynamically disordered aragonite with freely rotating CO3 groups, similar to that in the CaCO3-V phase with a calcite-like structure. Disarag has a stability field expanding from 3 to 10 GPa and from 1600 to 2000 K. Consideration of twinned structure enlarges this field, decreasing the transition temperature from aragonite to disarag at 100–300 K. At P–T parameters corresponding to the transition from aragonite to disarag, the marked disappearance of the diffraction peaks is observed in in situ experiments. We show that, among known phases of CaCO3, disarag is the best candidate for the explanation of this reconstruction of diffraction pattern. Also, for the first time, using ab initio molecular dynamics technique, we determine equilibrium curves between calcite and its disordered phases CaCO3-IV and CaCO3-V. We show that the transitions of alkaline-earth carbonates CaCO3, SrCO3, and BaCO3 to the disordered states start when the critical angle of librations of the CO3 group about the axis perpendicular to the molecular three-fold axis exceeds 45°. The calcite-like structure of CaCO3 is characterized by more intense librations than the aragonite-like structure of this compound and reaches the critical angle at lower temperatures. As a result, calcite transforms into the disordered state at lower temperatures than aragonite.

Orthocarbonates of Ca, Sr, and Ba—The Appearance of sp3-Hybridized Carbon at a Low Pressure of 5 GPa and Dynamic Stability at Ambient Pressure

“…In this case, high-quality settings were used: cutoff energy, 800 eV, k-point sampling grid of spacing, 0.2 Å –1 , and σ = 0.05 eV. The available experimental P – T phase diagrams of alkaline and alkaline-earth carbonates show that QHA correctly reproduces the monovariant equilibrium curves if the processes of dynamical disordering of [CO 3 ] atomic groups do not take place. ,− …”

Formation of Mg-Orthocarbonate through the Reaction MgCO3 + MgO = Mg2CO4 at Earth’s Lower Mantle P–T Conditions

“…For this task, the lattice vibration frequencies were calculated with the PHONOPY code . By our experience with the P – T phase diagrams of carbonates, this technique reliably reproduces phase boundaries in the wide temperature range, ,, up to 80–90% of the melting temperature, if the process of dynamical disordering does not take place.…”

Experimental-based mechanistic study and optimization of hydrothermal liquefaction of anaerobic digestates

“…Because aragonite is the most stable phase of CaCO 3 under high pressure, more-severe conditions (including higher pressures) can induce the phase transformation of calcite into aragonite (r37). 84 Meanwhile, the establishment and stabilization of vaterite under more severe conditions was promoted by increased production of hydrophilic organic macromolecules (r39), e.g., phenols, aldehydes, and ketones, 85 which may create hydrogen-bonded networks with water and deplete free H 2 O molecules. Consequently, the initially formed vaterite crystals did not readily transform into calcite and continued to aggregate and precipitate, forming more vaterites.…”