Optical transitions must preserve the total spin and occur only between levels of the same total spin. Specifically, transitions between the ground and excited states (with equal spin) can be induced using a green laser with a wavelength of 546 nm. Transitions E→A and E→A are non-radiative, while A →E has both a non-radiative and infrared decay path.
The diagram on the right shows the multi-electronic states of the NV center labeled according to their symmetry (E or A) and their spin state (3 for a triplet (S=1) and 1 for a singlet (S=0)). There are two triplet states and two intermediate singlet states.