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Orientation molecular dynamics were investigated in a series of “defect-free” oligofluorenes by depolarized dynamic light scattering and dynamic NMR spectroscopy. Typical liquid crystalline pretransitional dynamics were observed upon cooling the isotropic phase to the liquid crystalline phase with strong increase of the scattered intensity and slowing down of the characteristic time of the probed collective relaxation. This is well accounted for by the Landau-de Gennes theory, however, with a strong temperature dependence of the viscosity coefficient, reflecting the proximity of the glass transition. For the trimer the two transitions almost overlap and the molecular orientation coincide with the α-relaxation associated with the glass transition. The NMR measurements confirm that the time scale of the dynamics is completely governed by the glass process, yet the geometry of the motion is anisotropic, yielding order parameters ranging from 0.15 to 0.25 for the long axis in the liquid crystalline phase. The glass transition is therefore geometrically restricted with poorly ordered mesophase which is consistent with the weak transverse phonons in the light scattering experiment down to Tg+20 K. [ABSTRACT FROM AUTHOR]

The molecular dynamics of the aromatic core as well as the hydrocarbon side chains have been studied in a new kind of glass-forming discotic liquid crystal, based on a triphenylene core. It serves as a model compound in which only a limited number of degrees of freedom is activated at the glass transition. Slow motion with non-Arrhenius temperature dependence (α process) is associated with the axial motion of the discs around the column axis. The geometry of this rotation is found to be neither a simple threefold jump as suggested by the pseudo threefold symmetry of the substituted triphenylene core nor does it correspond to small-step rotational diffusion, established as a prominent feature of the rotational motions of polymers at the glass transition. Instead ill-defined angular displacements with pseudo threefold symmetry are detected by two-dimensional exchange NMR. A simple model combining small-step diffusion and rotational jumps is presented that quantitatively accounts for the angular displacements observed. The motional behavior and the conformational order of the side chains were also studied. This shows that the high frequency β process detected previously by dielectric spectroscopy indeed can be associated with side chain motions. Moreover evidence is presented that the axial motion of the discs is a cooperative process, where adjacent molecules within the column rotate in a correlated fashion without changing the conformation of the side chains in the immediate neighborhood of the core. [ABSTRACT FROM AUTHOR]

Theory and application are described of a new rotor-synchronized 3D-NMR (three-dimensional nuclear magnetic resonance) experiment, that correlates molecular structure, order, and dynamics in partially oriented solids. General expressions for the sideband intensities in three frequency dimensions are developed for uniaxially ordered samples undergoing ultraslow molecular motions. For an isotropic powder the exchange pattern is confined to a single plane perpendicular to one of the frequency axes. For a partially ordered solid without exchange the sideband pattern is confined to a cross-diagonal plane. Sidebands in the full 3D cube result only if the residue giving rise to the signal is involved in both, molecular order and dynamics. The experiment, therefore, correlates these two properties and relates them to the chemical structure. Moreover, it offers a means to exploit the superior information about the geometry of the molecular motions provided by partially ordered samples under high resolution magic angle spinning (MAS) conditions. The technique is illustrated by 3D MAS spectra of highly oriented poly(oxymethylene), where strong positive and negative sidebands in the full 3D cube result from the helical jump motion. [ABSTRACT FROM AUTHOR]

The two-dimensional (2D) exchange nuclear magnetic resonance (NMR) experiment is applied to study ultraslow as well as faster motions in powdered solids. The theoretical framework required for the simulation of 2D exchange of the faster motions, and for the evaluation of the experimental data, is developed. Calculations are presented for two standard models: two-site jump and isotropic rotational diffusion. For discrete jump motion, anisotropic spin-lattice relaxation during the mixing time is also considered. The resulting, simulated 2D line shapes show new characteristics in the intermediate dynamic range. Experimental data are presented for two-site exchange in the model compound polycrystalline dimethylsulphone. The technique is then applied to study the chain dynamics of linear polystyrene in the glass transition range. Close to Tg the correlation times extracted from 2D exchange NMR exhibit strong non-Arrhenius behavior. This data together with correlation times obtained at higher temperatures from conventional T1 data follows the WLF equation over 11 orders of magnitude, from 10-6 to 1000 s. It is shown that 2D exchange NMR and spin-lattice relaxation probe the α and the β process, respectively, of the chain dynamics in the glass transition region. [ABSTRACT FROM AUTHOR]

This letter presents the first direct measurement of the length scale of dynamic heterogeneity in a low molecular weight glass former without the perturbing effect of probe molecules or confinement. Using a multidimensional [sup 13]C solid-state exchange NMR experiment, 1 nm heterogeneities were found in glycerol for temperatures ranging from 199 K to 207 K (T[sub g]=189 K). This small size and weak temperature dependence allow some distinctions to be made among different models of the glass transition. It is shown that the dynamics are not influenced by a low concentration (0.1 wt. %) relaxation agent Cu(NO[sub 3])[sub 2]. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]