Theoretical Treatment of Degenerate Electron Exchange and Dimerization in Spin Dynamics of Radical Ion Pairs as Observed by Magnetic Field Effects

In this work we have compared manifestations of degenerate electron exchange (DEE) and dimerization reactions in MARY (magnetically affected reaction yield) spectroscopy and time-resolved magnetic field effects (TR-MFE) of radical ion pairs (RIPs). It is shown that dimerization results in phase and frequency changes of the quantum beats in TR-MFE traces, whereas DEE leads to relaxation-type changes in the spin dynamics of RIPs. Dimerization does not change the width of MARY lines considerably, but leads to new lines corresponding to dimer radical ions. In contrast, DEE substantially changes the MARY line widths. Our treatment provides ways to discriminate between both processes from experimental MARY spectra and TR-MFE kinetics. An experimental example dealing with concentration-dependent broadening of the MARY lines is also discussed.