Study of molecular motions in liquids by electron spin-lattice relaxation measurements,I: Semiquinone ions in hydrogen bonding solvents

The electron spin-lattice relaxation times (T ₁) of a variety of semiquinone ions in hydrogen bonding solvents have been measured by the pulsed saturation recovery technique as a function of temperature (T) and viscosity (η) of the solvent. Also linewidths (ΔH) have been measured in suitable cases in such solvents at low radical concentrations (～10^?4 M). It is observed that (i) the temperature and viscosity dependence ofT ₁ can be fitted to an equation of the form 1/T ₁=A(T/η)+Bexp(-ΔE/RT) whereA andB are constants and ΔE is an activation energy of the order of 1 kcal mole^?1 for these systems; (ii)T ₁ is essentially independent of the radical concentration within the range 10^?3 to 5×10^?2 M; (iii) the concentration independent part of the linewidth (ΔH) increases linearly with (η/T) at sufficiently low temperatures, and (iv) the (η/T) dependent part ofT ₁ is sensitive to the size of the semiquinone as well as that of the solvent molecule, whereas the linewidth which is proportional to (η/T) at high viscosity, low temperature region is not sensitive to the size of the semiquinone and that of the solvent. Based on these observations, it is postulated that in hydrogen bonding solvents, three types of motion contribute significantly to electron spin relaxation:

1. A restricted small step diffusional motion, not involving large changes in the orientation of the molecule, leading to the dominant viscosity dependent contributions toT ₁ and ΔH, due to spin rotation interaction;
2. a large amplitude reorientation of the semiquinone, coupled to translational diffusion, resulting in viscosity dependent contributions toT ₁ and ΔH, throughg-modulation;
3. a hindred rotation of the semiquinone within the solvent cage, contributing toT ₁ due to spin rotation interaction.

The fact thatT ₁ is not sensitive to the concentration of the radicals, is ascribed to the formation of the solvent cage that prevents the close approach of radicals, thereby rendering radical-radical interactions to be weak mechanisms for relaxation, even at relatively high radical concentrations.