AbstractIt is well known that NaCl salt crystals can easily dissolve in dilute aqueous solutions at room temperature. Herein, we reported the first computational evidence of a novel salt nucleation behavior at room temperature, i.e., the spontaneous formation of two-dimensional (2D) alkali chloride crystalline/non-crystalline nanostructures in dilute aqueous solution under nanoscale confinement. Microsecond-scale classical molecular dynamics (MD) simulations showed that NaCl or LiCl, initially fully dissolved in confined water, can spontaneously nucleate into 2D monolayer nanostructures with either ordered or disordered morphologies. Notably, the NaCl nanostructures exhibited a 2D crystalline square-unit pattern, whereas the LiCl nanostructures adopted non-crystalline 2D hexagonal ring and/or zigzag chain patterns. These structural patterns appeared to be quite generic, regardless of the water and ion models used in the MD simulations. The generic patterns formed by 2D monolayer NaCl and LiCl nanostructures were also confirmed by ab initio MD simulations. The formation of 2D salt structures in dilute aqueous solution at room temperature is counterintuitive. Free energy calculations indicated that the unexpected spontaneous salt nucleation behavior can be attributed to the nanoscale confinement and strongly compressed hydration shells of ions.