Intermolecular Spin Relaxation and Translation Diffusion in Liquids and Polymer Melts: Insight from Field‐Cycling1H NMR Relaxometry

Abstract

With the advent of commercial field-cycling (FC) spectrometers, NMR relaxometry has gained new momentum as a method of investigating dynamics in liquids and polymers. The outcome of FC NMR experiments is spin-lattice relaxation time versus frequency (relaxation dispersion). In the case of protons, due to the intra- and intermolecular origin of dipolar interactions, the relaxation dispersion reflects rotational as well as translational dynamics. The latter shows a universal dispersion law at low frequencies, which allows determination of the diffusion coefficient D(T) in addition to the rotational correlation time τ(rot)(T), that is, FC (1)H NMR becomes an alternative to field-gradient NMR spectroscopy. Subdiffusive translation found in polymers can be accessed by singling out the intermolecular relaxation through isotope dilution experiments, and the mean square displacement can then be revealed as a function of time, thus complementing neutron scattering experiments. Likewise, information on reorientational dynamics is provided by the intramolecular relaxation. Assuming frequency-temperature superposition the corresponding correlation functions can be monitored up to eight decades in amplitude and time, which allows thorough testing of current polymer theories.