Refined method for predicting electrochemical windows of ionic liquids and experimental validation studies.

A combined classical molecular dynamics (MD) and ab initio MD (AIMD) method was developed for the calculation of electrochemical windows (ECWs) of ionic liquids. In the method, the liquid phase of ionic liquid is explicitly sampled using classical MD. The electrochemical window, estimated by the energy difference between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), is calculated at the density functional theory (DFT) level based on snapshots obtained from classical MD trajectories. The snapshots were relaxed using AIMD and quenched to their local energy minima, which assures that the HOMO/LUMO calculations are based on stable configurations on the same potential energy surface. The new procedure was applied to a group of ionic liquids for which the ECWs were also experimentally measured in a self-consistent manner. It was found that the predicted ECWs not only agree with the experimental trend very well but also the values are quantitatively accurate. The proposed method provides an efficient way to compare ECWs of ionic liquids in the same context, which has been difficult in experiments or simulation due to the fact that ECW values sensitively depend on experimental setup and conditions.