Nuclear Spin Relaxation in Viscous Liquids: Relaxation Stretching of Single-Particle Probes

Spin-lattice relaxation rates R₁(ω,T), probed via high-field and field-cycling nuclear magnetic resonance (NMR), are used to test the validity of frequency–temperature superposition (FTS) for the reorientation dynamics in viscous liquids. For several liquids, FTS is found to apply so that master curves can be generated. The susceptibility spectra are highly similar to those obtained from depolarized light scattering (DLS) and reveal an excess wing. Where FTS works, two approaches are suggested to access the susceptibility: (i) a plot of deuteron R₁(T) vs the spin–spin relaxation rate R₂(T) and (ii) a plot of R₁(T) vs an independently measured reference time τ_ref(T). Using single-frequency scans, (i) allows one to extract the relaxation stretching as well as the NMR coupling constant. Surveying 26 data sets, we find Kohlrausch functions with exponents 0.39 < β_K ≤ 0.67. Plots of the spin–spin relaxation rate R₂─rescaled by the NMR coupling constant─as a function of temperature allow one to test how well site-specific NMR relaxations couple to a given reference process. Upon cooling of flexible molecule liquids, the site-specific dynamics is found to merge, suggesting that near T_g the molecules reorient essentially as a rigid entity. This presents a possible resolution for the much lower stretching parameters reported here at high temperatures that contrast with the ones that were reported to be universal in a recent DLS study close to T_g. Our analysis underlines that deuteron relaxation is a uniquely powerful tool to probe single-particle reorientation.