Interfacial ion hydration and electrostatics govern salt precipitation and crystal morphology

Abstract

Salt precipitation, a phenomenon central to processes such as soil salinization, water treatment, and energy storage, is dictated by nanoscale hydration and electrostatic interactions at crystal interfaces. Understanding how their interplay gives rise to salt-specific growth behaviors and morphologies remains a critical challenge. Combining large-scale molecular dynamics simulations with free energy calculations, we investigate the precipitation behavior of three common salts, namely, NaCl, KCl, and Na2SO4, on their respective crystal surfaces. While all crystals grow steadily under controlled supersaturation, their surface morphologies differ markedly. KCl grows in a nearly ideal layer-by-layer mode, whereas NaCl and Na2SO4 develop increasingly rough, defect-rich surfaces. This roughening is accompanied by an early-stage charge imbalance at the crystal surface, characterized by preferential cation adsorption. The resulting local electrostatic environment modifies the structuring and dynamics of interfacial water, which in turn facilitates the premature growth of subsequent layers. We further find that ion adsorption is strongly defect-dependent: kinks provide stabilizing environments, whereas steps are energetically unfavorable due to their distinct hydration. Our study offers molecular-level insight into the coupled roles of ion-specific adsorption and interfacial hydration in shaping crystal morphology for different salts.