The Relation Between Ejection Mechanism and Ion Abundance in the Electric Double Layer of Drops

The composition of outer drop layers has been associated with distinct chemical reactivity. We use atomistic modeling to examine how the composition of the surface excess charge layer (SECL) is related to the ejection mechanisms of ions. Even though the drop disintegration is inherently a non-equilibrium process we find that the equilibrium ion distribution in SECL predicts the ions that are ejected. The escape of the ions in aqueous drops takes place from conical protrusions that are global drop deformations and their appearance is independent of the location of a single ion. Our results are consistent with the equilibrium partition model, which associates the mass spectrum with the distribution of analytes in the drop’s double electric layer. We present evidence that atomistic simulations of minute nano-drops cannot distinguish Rayleigh fission from the ion evaporation mechanism.