Temperature Dependence of the Dielectric Properties and Dynamics of Ionic Liquids

Abstract

No solo dancers: The temperature dependence of dielectric spectra suggests that the lower‐frequency relaxation dominating the dynamics of imidazolium‐based room temperature ionic liquids cannot be solely due to independent rotational diffusion of the cations (see picture), but must also include cooperative motions of the surrounding particles.magnified image Dielectric spectra were measured for eight, mostly imidazolium‐based, room temperature ionic liquids (RTILs) over a wide range of frequencies (0.2≤ν/GHz≤89) and temperatures (5≤θ/°C≤ 65). Detailed analysis of the spectra shows that the dominant low frequency process centred at ca. 0.06 to 10 GHz (depending on the salt and the temperature) is better described using a symmetrically broadened Cole–Cole model rather than the asymmetric Cole–Davidson models used previously. Evaluation of the temperature dependence of the static permittivities, effective dipole moments, volumes of rotation, activation energies, and relaxation times derived from the dielectric data indicates that the low frequency process cannot be solely due to rotational diffusion of the dipolar imidazolium cations, as has been thought, but must also include other contributions, probably from cooperative motions. Analysis of the Debye process observed at higher frequencies for these RTILs is not undertaken because it overlaps with even faster processes that lie outside the range of the present instrumentation.