Spin evolution of radical pair with radical containing two groups of equivalent magnetic nuclei.

ABSTRACT

Analytical solution is obtained for time-resolved magnetic field effects (TR-MFE) on recombination fluorescence of radical-ion pair (RIP) containing radical ion with two groups of magnetically equivalent nuclei. The present theoretical approach is applied to three experimental systems RIPs containing radical cations of 2,3-dimethylbutane, 2,2,6,6-tetramethylpiperidine, or diisopropylamine and radical anion of p-terphenyl-d14 in nonpolar alkane solutions. Good agreement between theory and experiment is found for all the three systems, hyperfine coupling constants of radical cations are obtained by fitting the experimental TR-MFE traces. The potential of the TR-MFE technique for studying radical ions with nonequivalent nuclei is discussed in detail. The wide applicability of the theoretical model and the experimental technique make them useful for studying short-lived radical species that are often beyond the reach of the conventional electron paramagnetic resonance spectroscopy.