SYNOPSISThe motion of nitroxide spin probes and spin labels in amorphous polymers is studied below the glass transition temperature with a two-dimensional pulsed electron doubleresonance experiment. Polystyrene and a liquid crystalline side group polymer are studied using both spin probes and spin labels covalently bound to specific sites along the polymer chain. Two methyl acrylic polymers differing only in their side group structure and polyvinylacetate are compared and large differences in the molecular dynamics deduced from both the nuclear and the electron spin relaxation rates are observed as the glass transition is approached. The results demonstrate the complexity of small amplitude motion in simple polymers below the glass transition temperature and show that it is very sensitive to the packing in the polymer. 0 1996 John Wiley & Sons, Inc. Keywords: EPR spin label spin probe spin relaxation correlation time distributions electron double resonance amorphous polymers side group liquid crystalline polymer
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