Geometry and time scale of the complex rotational dynamics of amorphous polymers at the glass transition by multidimensional nuclear magnetic resonance

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Abstract
We present a new multidimensional NMR exchange experiment, three dimensional difference correlated exchange spectroscopy (DICO), which allows one to extract detailed information about the time scale as well as the geometry of rotational processes simultaneously. In contrast to experiments presently available the geometric information specified by a dynamic order parameter is independent of a specific model. Among others full isotropisation can be directly seen from the spectrum via a symmetry criterion. We apply this method to study the chain motion of polystyrene slightly above the glass transition. The DICO spectra prove that a typical chain segment performs small angle fluctuations as well as large angle jumps which can neither be described as random jumps nor tetrahedral jumps. A typical jump angle can be estimated to be of the order of 30°−40°.