As well as characterising the nucleation mechanisms far into the metastable solution zone, we also ruled out the PNC pathway for NaCl. Using umbrella sampling, we computed the equilibrium constant 𝐾 for ion pair association in the dilute limit. Despite the significant ion association that occurs in solutions across all of the metastable solutions investigated 𝑆 = 1 -4, the result that 𝐾 < 1 means that ion dissociation is thermodynamically favourable in dilute solutions and ion assembly into liquid-like clusters is due to non-idealities in the solution phase. These liquid-like entities can reach significant sizes, containing up to hundreds of ions at the high end of concentration, and evolve their topology rapidly over simulation timescales.