Influence of ion size asymmetry on the properties of ionic liquid-vapour interfaces

The influence of ion size asymmetry on the properties of ionic liquid-vapour interfaces is investigated using molecular dynamics simulations of the soft primitive model. Ion size asymmetry results in charge separation at the liquid-vapour interface and therefore in a local violation of the electroneutrality condition. For moderate size asymmetries the electrostatic potential at the interface can reach values of the order of 0.1 V. Size asymmetry plays a very important role in determining ion adsorption at the liquid-vapour interface of ionic mixtures. The interfacial adsorption of the bigger component results in an increase of the electrostatic potential, and a reduction of the interfacial surface tension. Our results show that ionic mixtures provide a very efficient way to tune the electrostatics and surface properties of ionic liquid-vapour interfaces.