Radical-induced hetero-nuclear mixing and low-field 13C relaxation in solid pyruvic acid

Radicals serve as source in dynamic nuclear polarization, but may also act as polarization sink. If the coupling between the electron spins and different nuclear reservoirs is stronger than any of the reservoirs' couplings to the lattice, radicals can mediate hetero-nuclear mixing. Here, we report radical-enhanced $^{13}$C relaxation in pyruvic acid doped with trityl. We find a linear dependence of the carbon $T_1$ on field between 5 mT and 2 T. We extend a model, employed previously for protons, to carbon, and predict efficient proton-carbon mixing via the radical Non-Zeeman reservoir, for fields from 20 mT to beyond 1 T. Discrepancies between the observed carbon relaxation and the model are attributed to enhanced direct hetero-nuclear mixing due to trityl-induced linebroadening, and a field-dependent carbon diffusion from the radical vicinity to the bulk. Measurements of hetero-nuclear polarization transfer up to 600 mT confirm the predicted mixing as well as both effects inferred from the relaxation analysis.
6 pages, 3 figures