Beams of fast N(S-4) atoms (10-1000 eV(lab)) were generated by charge transfer of N+ ions with Kr atoms. NH(A-X) chemiluminescence (CL) resulting from N + CH4 collisions was spectrally resolved. The CL cross-section was determined relative to the N+ + CH4 CL reaction. It is only half as large, but has a very similar energy dependence. NH(A) formation up to unusually high collision energies (> 200 eV(CM)) is explained by a 'billiard ball' model. Spectra of CH (A(2)Delta, B(2)Sigma (-), C(2)Sigma (+)) fragments were also observed at high energies. Computer simulations of the emission spectra from both the neutral and the ionic reaction yielded rovibrational populations. The differences are discussed.