An interatomic potential model for carbonates allowing for polarization effects

Abstract

An empirical model for investigating the behaviour of CaCO₃ polymorphs incorporating a shell model for oxygen has been created. The model was constructed by fitting to: the structure of aragonite and calcite; their elastic, static and high-frequency dielectric constants; phonon frequencies at the wave vectors [½ 0 2] and [0 0 0] of calcite; and vibrational frequencies of the carbonate deformation modes of calcite. The high-pressure phase transition between calcite I and II is observed. The potentials for the CO₃ group were transferred to other carbonates, by refitting the interaction between CO₃ and the cation to both the experimental structures and their bulk modulus, creating a set of potentials for calculating the properties of a wide range of carbonate materials. Defect energies of substitutional cation defects were analyzed for calcite and aragonite phases. The results were rationalized by studying the structure of calcite and aragonite in greater detail.