The dynamics of the H-displacement channel in the reaction N((2)D) + CH(4) has been investigated by the crossed molecular beam (CMB) technique with mass spectrometric detection and time-of-flight (TOF) analysis at five different collision energies (from 22.2 up to 65.1 kJ/mol). The CMB results have identified two distinct isomers as primary reaction products, methanimine and methylnitrene, the yield of which significantly varies with the total available energy. From the derived center-of-mass product angular and translational energy distributions the reaction micromechanisms, the product energy partitioning and the relative branching ratios of the competing reaction channels leading to the two isomers have been obtained. The interpretation of the scattering results is assisted by new ab initio electronic structure calculations of stationary points and product energetics for the CH(4)N ground state doublet potential energy surface. Differently from previous theoretical studies, both insertion and H-abstraction pathways have been found to be barrierless at all levels of theory employed in this work. A comparison between experimental results on the two isomer branching ratio and RRKM estimates, based on the new electronic structure calculations, confirms the highly nonstatistical nature of the N((2)D) + CH(4) reaction, with the production of the CH(3)N isomer dominated by dynamical effects. The implications for the chemical models of the atmosphere of Titan are discussed.