Analysis of EPR-time profiles of transient radicals with unresolved spectra

A method for analysing EPR-time profiles of transient radicals in solution with unresolved hyperfine structure is proposed. It is based on considering the magnetic field integral of the magnetization, i.e., the total EPR signal intensity, instead of single components of overlapping EPR transitions. For a radical system involving chemical kinetics, chemically induced electron polarization (CIDEP), and spin relaxation, an analytical solution is found for the evolution of the integral magnetization in the Laplace domain. The solution in the time domain is given for the case of negligible saturation, i.e., omega2(1)T1T2 < 1. The formulae presented are suitable to avoid equivocal multi-parameter fits when analysing the results of time-resolved continuous-wave EPR experiments for the observables, which characterize the chemical kinetics, CIDEP, and electron spin relaxation of radical systems.