Impact of molecular symmetry on crystallization pathways in highly supersaturated KH2PO4 solutions

Solute structure and its evolution in supersaturated aqueous solutions are key clues to understand Ostwald’s step rule. Here, we measure the structural evolution of solute molecules in highly supersaturated solutions of KH 2 PO 4 (KDP) and NH 4 H 2 PO 4 (ADP) using a combination of electrostatic levitation and synchrotron X-ray scattering. The measurement reveals the existence of a solution-solution transition in KDP solution, caused by changing molecular symmetries and structural evolution of the solution with supersaturation. Moreover, we find that the molecular symmetry of H 2 PO 4 - impacts on phase selection. These findings manifest that molecular symmetry and its structural evolution can govern the crystallization pathways in aqueous solutions, explaining the microscopic origin of Ostwald’s step rule.