Measurement of the rate of bimolecular electron spin relaxation between pairs of reactive radicals using time-resolved electron spin-echo spectroscopy

The time-resolved electron spin echo (ESE) method has been employed to measure the bimolecular contribution to electron spin relaxation in the acetate radical xCH2CO-2, formed by pulse radiolysis. Time-resolved ESE signals from solutions containing up to 4 x 10-4 M initial radical concentrations were analyzed using Bloch equations modified to include the effects of strong Heisenberg exchange, chemical reaction, and CIDEP. It is found that the electron exchange rate is approx.3 times faster than the chemical reaction rate, contrary to a simple model involving only statistical factors which predicts equal rates for the two processes. It is also found that the CIDEP enhancement factor is independent of initial radical concentration over the ten fold range of concentrations studied