What is the origin of slow relaxation modes in highly viscous ionic liquids?

Room temperature ionic liquids (RTILs) are molten salts consisting entirely of ions and have over the past decades gained increased interest due to their high potential in applications. These structurally complex systems often display multiple relaxation modes in the response functions at lower frequencies, hinting to complex underlying mechanisms. While the existence of these multimodal spectra in the shear mechanical, dielectric, and light scattering response of RTILs has been confirmed multiple times, controversy still surrounds the origin. This paper, therefore, aims to provide additional insights into the multimodal spectra seen in RTILs by presenting new shear mechanical results on seven different RTILs: Pyr1n-TFSI with n = 4, 6, and 8; Pyr18-TFSI mixed with Li-TFSI in two high concentrations; and Cn-mim-BF4 with n = 3 and 8. Dynamic depolarized light scattering was also measured on one of the Pyr18-TFSI Li-salt mixtures. These specific cases were analyzed in detail and put into a bigger perspective together with an overview of the literature. Recent literature offers two specific explanations for the origin of the multimodal shear mechanical spectra: (1) cation-anion time scale separation or (2) combined cation-anion relaxation in addition to a dynamic signal from mesoscale aggregates at lower frequencies. However, neither of these two pictures can consistently explain all the results on different ionic liquids. Instead, we conclude that the origin of the multimodal spectrum is system specific. This underlines the complexity of this class of liquids and shows that great care must be taken when making general conclusions based on specific cases.