Librational dynamics of nitroxide molecules in a molecular glass studied by echo-detected EPR

Nitroxides 2,2,6,6-tetramethyl-4-piperidone N-oxide (tempone), 3-carboxy-proxyl and potassium peroxylamine disulfonate (Fremy salt) in glycerol solution were studied in a wide temperature range near the glass transition temperatureT _g. The echo-detected (ED) electron paramagnetic resonance (EPR) lineshape reveals strong dependence on the time interval τ between the echo-forming microwave pulses which is readily explained by anisotropic phase relaxation. Employing a librational model of molecular motion and the Redfield relaxation theory, spectra were simulated for the τ’s varying in a large interval. The anisotropic relaxation rate increases with temperature increase and it is larger for nitroxide with a larger molecular size. The mean-squared amplitude of motion, obtained from reduced hyperfine splitting in continuous-wave EPR, near T_g linearly depends on temperature which is characteristic of harmonic solids. For tempone in a host crystal 2,2,4,4-tetramethyl-cyclobutan-1, 3-dione the anisotropic spin relaxation rate decreases with temperature increase so the found feature solely belongs to a glassy state. A new approach is proposed for modeling slow wobbling motion in a restricted angular space.