Conical Shape Fluctuations Determine the Rate of Ion Evaporation and the Emitted Cluster Size Distribution from Multicharged Droplets.

The ion evaporation mechanism (IEM) is perceived to be a major pathway for disintegration of multi-ion charged droplets found in atmospheric and sprayed aerosols. However, the precise mechanism of IEM and the effect of the nature of the ions in the emitted cluster size distribution have not yet been established despite its broad use in mass spectrometry and atmospheric chemistry over the past half century. Here, we present a systematic study of the emitted ion cluster distribution in relation to their spatial distribution in the parent droplet using atomistic modeling. It is found that in the parent droplet, multiple kosmotropic and weakly polarizable chaotropic ions (Cs) are buried deeper within the droplet than polarizable chaotropic ions (Cl, I). This differentiation in the ion location is only captured by a polarizable model. It is demonstrated that the emitted cluster size distribution is determined by dynamic conical deformations and not by the equilibrium ion depth within the parent droplet as the IEM models assume. Critical factors that determine the cluster size distribution such as the charge sign asymmetry that have not been considered in models and in experiments are presented. We argue that the existing IEM analytical models do not establish a clear difference between IEM and Rayleigh fission. We propose a shift in the existing view for IEM from the equilibrium properties of the parent droplet to the chemistry in the conical shape fluctuations that serve as the centers for ion emission. Consequently, chemistry in the conical fluctuations may also be a key element to explain charge states of macromolecules in mass spectrometry and may have potential applications in catalysis due to the electric field in the conical region.