Dynamic nuclear polarization weighted spectroscopy of multispin electronic-nuclear clusters

Nuclear spins and paramagnetic centers in a solid randomly group to form clusters featuring nearly degenerate, hybrid states whose dynamics are central to processes involving nuclear spin-lattice relaxation and diffusion. Their characterization, however, has proven notoriously difficult mostly due to their relative isolation and comparatively low concentration. Here, we combine magnetic field cycling experiments, optical spin pumping, and variable radiofrequency (RF) excitation to probe transitions between hybrid multispin states formed by strongly coupled electronic and nuclear spins in diamond. Leveraging bulk nuclei as a collective time-integrating sensor, we probe the response of these spin clusters as we simultaneously vary the applied magnetic field and RF excitation to reconstruct multidimensional spectra. We uncover complex nuclear polarization patterns of alternating sign that we qualitatively capture through analytical and numerical modeling. Our results unambiguously expose the impact that strongly hyperfine-coupled nuclei can have on the spin dynamics of the crystal, and inform future routes to spin cluster control and detection.