© 2016. The American Astronomical Society. All rights reserved. The branching ratios for the N(4S) + N(2D), N(4S) + N(2P), and N(2D) + N(2D) channels are measured for the photodissociation of in the vacuum ultraviolet (VUV) region of 100,808-122,159 cm-1 using the VUV-VUV pump-probe approach combined with velocity-map-imaging-photoion detection. No evidence of forming the ground-state N(4S) + N(4S) products is found. No potential barrier is observed for the N(2D) + N(2D) channel, but the N(4S) + N(2P) channel has a small potential barrier of ≈740 cm-1. The branching ratios are found to depend on the symmetry of predissociative N2 states instead of the total VUV excitation energy, indicating that N2 photodissociation is nonstatistical. When the branching ratios for N(4S) + N(2D) and N(4S) + N(2P) products are plotted as a function of the VUV excitation energy for the valence N21Πu and states, oscillations in these ratios are observed demonstrating how these channels are competing with each other. These data can be used to select both the velocity and internal states of the atomic products by picking the quantum state that is excited. High-level ab initio potential energy curves of the excited N2 states are calculated to provide insight into the mechanisms for the observed branching ratios. The calculations predict that the formation of both N(4S) + N(2D) and N(4S) + N(2P) channels involves potential energy barriers, in agreement with experimental observations. A discussion of the application of the present results to astronomy, planetary sciences, and comets is given.