Temperature-dependent hyperfine coupling constants in electron spin resonance

Abstract
The temperature dependence of the hydroxyl proton splittings in the radical cation of 1,2,4,5-tetrahydroxybenzene has been measured over the temperature range -80°C to +60°C. The ring proton splittings show no significant dependence upon temperature. The hyperconjugative contribution to the hydroxyl proton coupling has been calculated as a function of temperature for a range of values of V 0, the two-fold barrier to rotation of an individual hydroxyl group, using numerical solutions to the Mathieu equation. This, together with the results of McLachlan SCF-MO calculations for this system, leads to a value of V 0 of 24 ± 2 kJ mol-1 and to an estimate of the spin-polarization parameter Q OHH of -3·87 ± 0·05 mT.