  Nanodiamonds containing nitrogen vacancy (NV-) centers show promise for a
number of emerging applications including targeted in vivo imaging and
generating nuclear spin hyperpolarization for enhanced NMR spectroscopy and
imaging. Here, we develop a detailed understanding of the magnetic resonance
behavior of NV- centers in an ensemble of nanodiamonds with random crystal
orientations. Two-dimensional optically detected magnetic resonance
spectroscopy reveals the distribution of energy levels, spin populations, and
transition probabilities that give rise to a complex spectrum. We identify
overtone transitions that are inherently insensitive to crystal orientation and
give well-defined transition frequencies that access the entire nanodiamond
ensemble. These transitions may be harnessed for high-resolution imaging and
generation of nuclear spin hyperpolarization. The data are well described by
numerical simulations from the zero- to high-field regimes, including the
intermediate regime of maximum complexity. We evaluate the prospects of
nanodiamond ensembles specifically for nuclear hyperpolarization and show that
frequency-swept dynamic nuclear polarization may transfer a large amount of the
NV- center's hyperpolarization to nuclear spins by sweeping over a small region
of its spectrum.
