Variation in Properties of Pre-Nucleation Calcium Carbonate Clusters Induced by Aggregation: A Molecular Dynamics Study

Abstract

Numerous studies have speculated calcium carbonate (CaCO3) nucleation induced by pre-nucleation clusters (PNCs) aggregation. However, it is challenging for experiments to directly obtain the relationship between PNCs aggregation and nucleation. Herein, we employ molecular dynamics simulations to explore the variation during PNCs aggregation, which can describe the beginning stage of CaCO3 nucleation induced by PNCs aggregation in supersaturated solutions. The results reveal that the formation of CaCO3 nucleus consists of PNCs spontaneous growth, PNCs solubility equilibrium, and aggregation of PNCs inducing nucleation. The PNCs aggregation, accompanied by the variation in the configuration and stability of CaCO3 aggregate, breaks the solubility equilibrium of PNCs and creates conditions for the formation of the more stable nucleus. Besides, the CaCO3 nucleus with the higher coordination number and the lower hydration number form when decreasing the CaCO3 concentration or increasing the temperature. This work not only sheds light on the formation of the CaCO3 nucleus but also contributes to the explanation for CaCO3 polymorphism.