We have studied details of the molecular origin of slow secondary relaxation near T(g) in a series of neat polyalcohols by means of dielectric spectroscopy and (2)H NMR. From glycerol to threitol, xylitol, and sorbitol the appearance of the secondary relaxation changes gradually from a wing-type scenario to a pronounced beta peak. It is found that in sorbitol the dynamics of the whole molecule contributes equally to the beta process, while in glycerol the hydrogen bond forming OH groups remain rather rigid compared to the hydrogens bonded to the carbon skeleton.

The small-molecule glass former methyl tetrahydrofuran ͑MTHF͒ was investigated using dielectric spectroscopy, spin-lattice relaxometry, multidimensional stimulated-echo nuclear magnetic resonance techniques, and field gradient diffusometry. We show experimentally that MTHF nicely fits into the pattern of related small-molecule glass-forming liquids, including the existence of a high-frequency contribution to the dielectric loss, the appearance of a pronounced translational enhancement, the dominance of small average rotational jump angles, and the existence of short-lived dynamical heterogeneity.

Proton, deuteron, and carbon NMR methods were applied to study various isotopic species of supercooled and glassy propylene carbonate. The molecular diffusion was investigated via static field gradient diffusometry and yielded evidence for a particularly pronounced enhancement of the translational over the reorientational dynamics. The latter was monitored using measurements of spin−lattice relaxation times and of two−time stimulated echoes. The sinâ€"sin correlation functions exhibited a pronounced dependence on the evolution times. From these results it is concluded that the geometry of molecular reorientation can be described as a superposition of moderately small jump angles (about 30˚) and a quasi−diffusive component which is responsible for about one−third of the total angular displacement. Finally, four−time stimulated echoes confirmed that the nonexponential relaxation in propylene carbonate is dynamically heterogeneous in nature. ©2000 American Institute of Physic

Study of the heating effect contribution to the nonlinear dielectric response of a supercooled liquid Primary and secondary relaxations in supercooled eugenol and isoeugenol at ambient and elevated pressures: Dependence on chemical microstructureWe have studied details of the molecular dynamics in a series of pure polyalcohols by means of dielectric spectroscopy and 2 H nuclear magnetic resonance ͑NMR͒. From glycerol to threitol, xylitol and sorbitol a systematic change in the dynamics of the primary and secondary relaxation is found. With increasing molecular weight and fragility an increase in the width of the ␣-peak is observed. Details of the molecular reorientation process responsible for the ␣-relaxation were exploited by two-dimensional NMR experiments. It is found that in the same sequence of polyalcohols the appearance of the secondary relaxation changes gradually from a wing type scenario to a pronounced ␤-peak. From NMR experiments using selectively deuterated samples the molecular origin of the secondary relaxation could be elucidated in more detail.

Spin-lattice relaxation rates R 1 (ω,T), probed via highfield 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 R 1 (T) vs the spin−spin relaxation rate R 2 (T) and (ii) a plot of R 1 (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 R 2 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 sitespecific 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.