Abstract
This work uses a recently proposed methodology to calculate the free energies of calcite and aragonite interfaces with water. This method properly includes the entropic contributions, ignored or approximated in previous work. By including this entropic component, we show that the aqueous calcite {101̅4} surface has a lower free energy than any of the aragonite surfaces. This resolves the discrepancies in previous simulation work that suggested that an aragonite nucleus would be more stable than a calcite one. Our analysis of the water structure highlights the generally greater entropic contribution to the interfacial free energy at the aragonite/water interface than at the calcite one. These methods are applied to a range of temperatures to examine how the solution temperature alters the interfacial energies. Our results are then discussed in the context of calcium carbonate nucleation and polymorph-morphology selection under different environmental conditions.