The Role of Concentration in Determining NaCl Nucleation Mechanism: A Story of Pathways Coexistence

Abstract: Deciphering the microscopic details of crystal nucleation remains a key open problem in chemical physics. For aqueous sodium chloride (NaCl), the extent to which nucleation involves amorphous ion aggregation, and the supersaturation regime in which two-step-like behavior emerges, remains actively debated. In this work, we examine NaCl nucleation at 12, 13, and 14 mol/kg ($S = 3.2, 3.5, 3.8$) using unbiased path sampling with $\infty$RETIS. Through a combination of reaction coordinate analysis, joint and conditional probability distributions, diffusion tensor analysis, and conditional free energy landscapes, we identify nucleation pathways without a priori mechanistic assumptions. While all concentrations are governed by the same reaction coordinate, indicating that nucleus growth and structural ordering are central to crossing the barrier, the nature of reactive trajectories changes with supersaturation. At lower concentrations, nucleation mainly occurs via tightly coupled increases in cluster size and ordering, compatible with a one-step-like mechanism. As concentration increases, amorphous aggregation becomes increasingly decoupled from crystallization, and pathways involving substantial amorphous growth prior to crystallization become progressively more probable. Importantly, these pathways coexist within a single broad reaction channel rather than proceeding through distinct metastable intermediate states. Together, these results reconcile earlier, contradictory reports on NaCl nucleation mechanisms and support a view of nucleation as an ensemble of competing reactive pathways whose relative probabilities vary continuously with supersaturation. More broadly, our findings illustrate that substantial mechanistic diversity can emerge within a classical nucleation framework, without requiring distinct non-classical descriptions.