Electron spin-lattice relaxation in solid ethanol: Effect of nitroxyl radical hydrogen bonding and matrix disorder

Abstract

The electron spin-lattice relaxation of 2,2,6,6-tetramethyl-1-piperidine-1-oxyl and 4-oxo-2,2,6,6-tetramethyl-1-piperidine-1-oxyl was measured at temperatures between 5 and 80 K in crystalline and glassy ethanol using $X$-band electron paramagnetic resonance spectroscopy. The experimental data at the lowest temperatures studied were explained in terms of electron-nuclear dipolar interaction between the paramagnetic center and the localized excitations, whereas at higher temperatures low-frequency vibrational modes from the host matrix and Raman processes should be considered. The strong impact of hydrogen bonding between the dopant molecule and ethanol host on the spin relaxation was observed in ethanol glass whereas in crystalline ethanol both paramagnetic guest molecules behaved similarly.