Structural transitions of calcium carbonate by molecular dynamics simulation

Calcium carbonate (CaCO3) plays a crucial role in the global carbon cycle, and its phase diagram is of significant scientific interest. We used molecular dynamics to investigate selected structural phase transitions of calcium carbonate. Using the Raiteri potential, we explored the structural transitions occurring at the constant pressure of 1 bar, with temperatures ranging from 300 to 2500 K, and at the constant temperature of 1600 K, with pressures ranging from 0 to 13 GPa. With increasing temperature, the transitions between calcite, CaCO3-IV, and CaCO3-V were characterized. In the calcite structure, the carbonate ions are ordered in a planar triangular arrangement, alternating with layers of calcium ions. As the temperature increases, the transition from calcite to CaCO3-IV occurs, leading to partial disordering of the carbonate ions. At higher temperatures, CaCO3-IV transforms into CaCO3-V. Through free energy analysis, we classified the latter transition as a continuous phase transition. At a temperature of 2000 K, a "disordered CaCO3" structure appears, characterized by low order within the calcium and carbonate sublattices and the free rotation of the carbonate ions. With increasing pressure, two calcium carbonate transformations were observed. At P = 2 GPa, the CaCO3-V phase undergoes a phase transition into CaCO3-IV, demonstrating that the model can describe the transition between these two phases as pressure- and temperature-driven. At P = 4.25 GPa, CaCO3-IV undergoes a phase transition into the CaCO3-Vb phase. This transition is classified as first-order based on free energy calculations.