Observation of the Pockels Effect in Ionic Liquids and Insights into the Length Scale of Potential-Induced Ordering.

Ionic liquids (ILs) under electric fields play essential roles in the electrochemical utilization of ILs. Recently, long-range organization of ILs in the vicinity of charged (and even neutral) surfaces has been revealed, but experimental evidence for such an ordering is still limited and its spatial length scale remains controversial. Here, we use confocal Raman microspectroscopy to investigate the effect of an applied electric potential on the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and its analogues in a space-resolved manner. Much to our surprise, the observed Raman difference spectra of the ILs obtained with and without an applied potential exhibit uniform intensity changes independent of vibrational modes of cations and anions, a finding in sharp contrast with the electric field effects on molecular liquids that we have previously observed. We interpret this unexpected finding in terms of the Pockels effect that occurs as a result of a potential-induced ordering of the IL near an IL-electrode interface. The refractive index changes due to the applied potential are estimated using the experimental Raman intensity changes. The results allow us to deduce that the length scale of the ordering in the ILs is tens to hundreds of nanometers, extending more than would be expected for the electrical double layer but not as far as a micrometer scale.