Prenucleation Cluster Pathway is Inconsistent with CaCO₃ Kinetics

It has been debated whether CaCO₃ nucleates classically with the attainment of a critical cluster size or nonclassically with the restructuring of a prenucleation cluster (PNC). Here, we determine from the nucleation kinetics of CaCO₃ that the transition state is composed of about 10 formula units, irrespective of the supersaturation. Crucially, the size of the transition state is considerably smaller than the average PNC size estimated from experimental characterization. This size discrepancy suggests the PNCs are uninvolved in nucleation, and the kinetics indicate that if CaCO₃ nucleates classically, the transition state must be an abnormally unstable (antimagic) cluster.