A model for solvated ion emission from electrospray droplets.

A model is presented which shows that the energy required to emit small singly charged and large multiply charged (protein) solvated ions from electrospray droplets can be considerably lower than those predicted by earlier models. By allowing the droplet surface to distort in reaction to the emerging ion, a more nuanced picture of the ion emission mechanism appears, one that covers the range from pure ion evaporation (PIE) for small ions to what may be termed activated pseudo-Rayleigh ion release (PRIR), a mechanism that yields charge states nearly indistinguishable from the charge residue model (CRM), for large ions. Predictions based on this model are qualitatively consistent with many experimentally observed trends.