Charge transport in ionic liquids contained in unidirectional nanoporous membranes (pore diameters: 7.5–10.4 nm) is investigated by combining broadband dielectric spectroscopy (BDS) and pulsed field gradient (PFG)-NMR. This enables one to determine the diffusion coefficient and the diffusion rate over more than 13 decades and to trace its temperature dependence. Under conditions of nanometric confinement, a change from a Vogel–Fulcher–Tammann into an Arrhenius-like thermal activation is observed, resulting in an enhancement of diffusivities by more than two orders of magnitude. The effect becomes more pronounced with decreasing pore diameter. It is attributed to changes in molecular packing and hence in density leading to higher mobility and electrical conductivity.

Polymer Dynamics: While free surfaces should allow polymer chains to move faster than in the bulk, the presence of a substrate might slow down the motion if there is an attraction between the two. Tress et al. (p. 1371 ; see the Perspective by Russell ) used dielectric spectroscopy to study “polymer islands” deposited on a substrate from dilute solution, where some islands contained just a few or only one polymer chain. The confinement of the polymer chain to small-surface geometries had virtually no influence on the dynamics of the polymers, aside from the segments in direct contact with the substrate.

Infrared Transition Moment Orientational Analysis (IR–TMOA) and Broadband Dielectric Spectroscopy (BDS) are combined to study molecular order and dynamics of the glass-forming liquid Tris(2-ethylhexy)phosphate (TEHP) confined in uni-directional nanopores with diameters of 4, 8, and 10.4 nm. The former method enables one to determine the molecular order parameter of specific IR transition moments. It is observed that the central P=O moiety of TEHP has a weak orientational effect (molecular order parameter S _z = −0.1 ± 0.04) due the nanoporous confinement, in contrast to the terminal C–H groups. BDS traces the dynamic glass transition of the guest molecules in a broad spectral range and at widely varying temperature. An enhancement of the mobility takes place when approaching the glass transition temperature and becomes more pronounced with decreasing pore diameter. This is attributed to a slight reduction of the density of the confined liquid caused by the 2-dimensional geometrical constraint.

A combination of PALS and BDS data revealed the development of negative pressure, due to vitrification of the interfacial molecules, and the behavior of the confined samples can be predicted from E_V/H_p of the bulk material.