Fragmentation modeling of gas-phase ionic liquid clusters in high-voltage electric field

Abstract

Cluster fragmentation subjected to a high-voltage electric field may play an important role in controlling the novel ionic liquid (IL) electrospray propulsion but has received little attention. In this work, the micro-fragmentation mechanisms of three kinds of IL clusters are numerically investigated using both static and dynamic approaches based on the quantum mechanical principles. Firstly, it reveals that the Coulomb interaction dominates the total inter-fragment energy for all three IL dimers, whereas the hydrogen-bonding interaction is identified as the main cause for the much slower break-up rate of the 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM-BF4]) dimer. In addition to the electrostatic interaction, the van der Waals interaction is a secondary energy component to which only a small fraction of atoms contribute significantly, regardless of IL cluster type. We find, only when the applied electric field is larger than 1 V/nm, the total inter-fragment energies of all three IL clusters start to dramatically reduced, indicating the possible occurrence of massive break-up. Secondly, ab initio molecular dynamics simulation further confirms that the [EMIM-BF4] negatively charged dimer is the most stable of three IL clusters under the identical conditions. As far as the high-voltage electric field is concerned, the one-parameter exponential function of break-up ratio versus time, routinely used in the field-free region, is not valid. Finally, on the basis of simulated results, a compound exponential-decay model is proposed, and the derived differential-sum equations from constant electric fields can be further applied to the non-uniform electric field.