Molecular Dynamics Simulations of 1-Ethyl-3-methylimidazolium Bis(trifluoromethyl)sulfonylimide Clusters and Nanodrops

BD Prince and P Tiruppathi and RJ Bemish and YH Chiu and EJ Maginn, JOURNAL OF PHYSICAL CHEMISTRY A, 119, 352-368 (2015).

DOI: 10.1021/jp507073e

Atomistic molecular dynamics simulations of small clusters and nanodroplets of the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethyl)sulfonylimide EMIM-Tf2N subject to an external electric field were performed. A 125-ion-pair droplet was found to be nearly spherical with an isotropic distribution of cations and anions under vacuum conditions. The droplet was subjected to external electric fields of varying strength, and ion emission events were observed. The initially spherical droplet is elongated along the electric field axis, resulting in nonspherical behavior and increased net dipole values after the application of strong electric fields. The critical electric field required for ion field emission was determined to be 0.985 V/nm, in agreement with the experimental value of 1.0 V/nm. Excellent agreement is found in the prediction of ionic emission products for a neutral 125 -ion-pair droplet of the ionic liquid at an electric field strength of 1.2 V/nm when compared to the results of two independent experiments. Small ionic liquid clusters were investigated with respect to their thermal stabilities and were found to be thermally stable well above room temperature. The role of electric fields in the dissociation of small charged ion clusters was also investigated.

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