The microscopic model and most optical properties of ensembles of the NV centers have been firmly established in the 1970s based on the optical measurements combined with uniaxial stress and on the electron paramagnetic resonance. However, a minor error in EPR results (it was assumed that illumination is required to observe NV EPR signals) resulted in the incorrect multiplicity assignments in the energy level structure. In 1991 it was shown that EPR can be observed without illumination, which established the energy level scheme shown above. The magnetic splitting in the excited state has been measured only recently.
The characterization of single NV centers has become a very competitive field nowadays, with many dozens of papers published in the most prestigious scientific journals. One of the first results was reported back in 1997. In that paper, it was demonstrated that the fluorescence of single NV centers can be detected by room-temperature fluorescence microscopy and that the defect shows perfect photostability. Also one of the outstanding properties of the NV center was demonstrated, namely room-temperature optically detected magnetic resonance.