Multiscale modeling of fragmentation in an electrospray plume

Abstract

We present a 3D-particle-in-cell (PIC) approach to modeling electrospray plumes typical of those formed by externally wetted emitter devices. Numerical grid-resolution techniques suitable for capturing strong electric fields in the emitter region were explored, and grid refinement criteria were quantified. The molecular dynamics simulations of the EMIM−BF4 ionic liquid system were modeled to determine the fragmentation mechanism in the presence of an electric field and dimer temperature as well as to provide fragmentation rates for the PIC simulations. An energy analysis of the molecular dynamics (MD) fragmentation demonstrated that the key mechanism for dimer fragmentation corresponds to a decrease in the Coulomb energy between the cation and anion in the system and that dimers of temperatures 300 and 600 K are extremely stable for electric fields smaller than 1.5 V/nm. Using probabilities of fragmentation consistent with the MD simulations, we implemented a dimer fragmentation model in our PIC simulations. The ion energy distribution functions obtained from the PIC simulations were used to predict retarding potential analysis (RPA) curves that were compared directly to measurements. The sensitivity of the RPA shape to the fragmentation probability was found to be significant. By comparing predicted and measured RPA curves for both negative and positive operation modes, and the fact that dimers do not fragment for electric fields less than 0.6 V/nm, we conclude that fragmentation of dimers occurs spontaneously due to their high thermal energies.